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EPA 905/4-87-003
6LNPO Report No. 87-11
July 1987
1982 Detroit Michigan
Area Sediment Survey
Prepared by
Pranas E. Pranckevicius
Remedial Program Staff
Great Lakes National Program Office
United States Environmental Protection Agency
for
U.S. Environmental Protection Agency
Great Lakes National Program Office
230 South Dearborn Street
Chicago, Illinois 60604
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FOREWORD
The Great Lakes National Program Office (GLNPO) of the United States
Environmental Protection Agency was established in Region V, Chicago,
to focus attention on the significant and complex natural resource
represented by the Great Lakes.
GLNPO implements a multi-media environmental management program drawing
on a wide range of expertise represented by universities, private firms,
State, Federal, and Canadian governmental agencies, and the International
Joint Commission. The goal of the GLNPO program is to develop programs,
practices and technology necessary for a better understanding of the
Great Lakes Basin ecosystem, and to eliminate or reduce to the maximum
extent practicable the discharge of pollutants into the Great Lakes system,
GLNPO also coordinates the United States' actions in fulfillment of the
Agreement between Canada and the United States of America on Great Lakes
Water Quality of 1978.
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DISCLAIMER
This report has been reviewed by the Great Lakes National Program Office,
United States Environmental Protection Agency, and approved for publication,
Approval does not signify that the contents necessarily reflect the views
and policies of the U.S. Environmental Protection Agency, nor does mention
of trade names or commercial products constitute endorsement or recommenda-
tion for use.
m
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ABSTRACT
Twenty-eight sediment grab samples from the western bank of the Detroit
River and three of its tributaries were chemically analyzed. Sampling
sites were chosen to find worst-case conditions. High levels of conven-
tional pollutants and metals were found throughout most of the study area.
Hydrophobic organic contaminants found in a wide range of concentrations
included: polynuclear aromatic hydrocarbons, polychlorinated biphenyls,
various pesticides, and volatile organic compounds. Contaminant distribu-
tions suggest recent inputs from local sources. Highest contaminant levels
were found in the Rouge River, the northern Trenton Channel and Conners
Creek in the Belle Isle Area. The City of Detroit Wastewater Treatment
Plant, combined sewer overflows, local steel and chemical industry and oil
refineries are implicated as likely sources. Several contaminants including
volatile organics, PCBs and hexachlorobenzene, seem to have major upstream
sources, perhaps in Lake St. Clair or the St. Clair River.
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TABLE OF CONTENTS
Page
FOREWORD
DISCLAIMER
ABSTRACT
TABLES
FIGURES
ACKNOWLEDGEMENTS
Summary and Conclusions
INTRODUCTION
Harbor Sediment Program
Sampling Methodology
Sampling Equipment
Analytical Methodology
Metals
Quality Assurance
SETTING
Urban and Industrial Development
Geology and Hydrogeology
Hydrology
Mineralogy
RESULTS AND DISCUSSION
Sampling Sites and Reporting
Field Observations
Conventional Pollutants
Organic Contaminants
Polynuclear Aromatic Hydrocarbons (PAHs)
PCBs
Pesticides
Volatile Organics
Phenolics
Substituted Benzenes and Substituted Cyclic Ketones
(Chlorinated Benzenes)
Phthalate Esters
ii
iii
iv
vi
vii
viii
1
6
9
10
10
11
13
14
14
15
16
17
19
20
28
28
32
36
38
39
39
40
REFERENCES
APPENDIX A:
APPENDIX B:
APPENDIX C:
APPENDIX D:
Guidelines for the Pollutional Classification
of Great Lakes Harbor Sediments
Analytical Method Documentation and Data Quality Assessment
Tables
Figures
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TABLES
PAGE
Table 1. Organic compounds sought in sediments by the GC/MS Cl-5
method and maximum detection limits
Table 2. Pesticides and PCBs sought in sediments by the GC/EC C6
method
Table 3. Metals analyzed and their detection limits C7
Table 4. Field observations C8
Table 5. Conventional pollutants C9
Table 6. Metals CIO
Table 7. Trace metals Cll
Table 8. Major metals C12
Table 9. Metals summary C13
Table 10. Organics summary table C14
Table 11. Polyaromatic Hydrocarbons (PAHs) (A) and (B) C15-16
Table 12. Hazardous PAHs C17
Table 13. Polychlorinated Biphenyls (PCBs) CIS
Table 14. DDT and metabolites C19
Table 15. Pesticides C20
Table 16. Volatile organics (A) and (B) C21-22
Table 17. Phenols C23
Table 18. Substituted benzenes, substituted cyclic ketones and C24
polycyclic aromatics.
VI
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FIGURES
Figure 1.
Figure 2.
Figure 3.
Figure 4.
Figure 5.
Figure 6.
Figure 7.
Figures 8 -
Figures 15 -
Figures 38 -
Figures 48 -
Figure 52.
Figure 53.
Figure 54.
Figure 55.
Figure 56.
Figure 57.
Figure 58.
Figure 59.
Figure 60.
PAGE
Detroit area industry 01
Bedrock surface topography D2
Detroit River study area 03
Hydrographs 04
Detroit 1982 sediment sampling sites 05
Huron River sediment sampling sites 06
Detroit Area Combined Sewer Overflows (CSOs) D7
14. Conventional Parameters 08-9
37. Metals D9-15
47. Polynuclear Aromatic Hydrocarbons 015-17
51. Polychlorinated Biphenyls (PCBs) 018
Gamma Chlordane 019
Beta - BHC 019
Dichloromethane 019
Trichloromethane 019
Phenol 020
Para-cresol 020
Hexachlorobenzene (HCB) 020
Dibenzofuran 020
Bis(2-ethy1 hexyl)phtha!ate D21
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ACKNOWLEDGEMENTS
The direction and extensive review of Mr. Vacys J. Saulys, Remedial
Programs Staff Chief at fireat Lakes National Program Office, and
Mr. Anthony G. Kizlauskas, USEPA Region V Dredging Expert are greatly
appreciated.
The author wishes to acknowledge the cooperation and assistance of
several other persons who have contributed to the development of this
report:
Mr. Larry Fink for his advice on matters relating to organic chemistry,
and his peer review of the report.
Mr. Frank Horvath, Michigan Department of Natural Resources, for his
review of the report.
Dr. John Hartig, International Joint Commission, for his review of the
report.
Mr. navid PeVault for his advice concerning laboratory quality
assurance.
Mr. .lohn Forwalter for his editorial assistance.
Ms. Rosetta McPherson, and Mr. Walter V. Jessering for data entry and
editing.
Special thanks go to Ms. Aldona fiaizutis and Ms. Raynell Whatley and
Ms. Dianne Watts for their patience and typing support.
vi ii
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SUMMARY
The objective of the 1982 Detroit, Michigan Sediment Survey was to
determine the degree of contamination of the river and harbor sediments
by toxic substances. Sediments in areas of suspected contamination along
the western side of the Detroit River, and in the major tributaries on the
western shore of the Detroit River were sampled. Sediment contaminant
data generated by this study will be used for reporting on the environ-
mental status of the area and identification of problem areas requiring
remedial activity.
Sampling site locations were chosen in areas where contaminanted sediments
were most likely to be found. Locations of industrial and municipal out-
falls and other suspected sources of contamination to river sediments
strongly affected decisions, as did sedimentation patterns and existing
sediment quality data. Sixty-five samples were retrieved. Of these,
twenty-eight samples were analyzed. 1982 Detroit sediment contaminant
levels were evaluated in terms of USEPA (1977) Sediment Guidelines for the
Pollutional Classification of Great Lakes Harbor Sediments, Appendix A
(Sediment Guidelines), where possible. However, these guidelines for pol-
lutional classification have been set for only 18 of the 109 parameters
which were analyzed. As no other guidelines exist, evaluation of the sev-
erity of contamination by the remaining 91 parameters required individual
interpretation.
CONVENTIONAL POLLUTANTS
Comparison of the concentrations of conventional pollutants against the USEPA
Sediment Guidelines indicates that sediments at all stations sampled and
analyzed by EPA GLNPO in 1982 in the Detroit area were highly contaminated
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with a few exceptions: Some stations in the area from Belle Isle to down-
town Detroit (PTR8P-D1, nTR82-OSA, and DTRR2-13), and all stations in the
Huron River area had moderate to low levels of contamination. The highest
levels of ammonia, total volatile solids, chemical oxygen demand (COP),
total Kjeldahl nitrogen (TKN), and cyanide were found in the Rouge River
downstream from the Dearborn Ford Plant. Phosphorus levels were highest
in the southern Trenton Channel. Oil and grease levels were highest in
the northern Trenton Channel, north of Belle Isle in Conners Creek, and in
the Rouge River.
METALS
Comparison of concentrations of heavy metals against. Sediment Guidelines
shows that the sediments were highly contaminated throughout most of the
study area. The only exceptions were stations PTR82-01 and PTR82-05A near
Belle Isle, and the three stations in the Huron River area.
Three portions of the study area had particularly high levels of certain
metals, possibly indicating sources in those areas or upstream: 1) Conners
Creek, in the Belle Isle area, ?) Rouge River, 3 ) northern Trenton Chan-
nel. Lead and barium were very high in Conners Creek. Iron and cadmium
concentrations were notably high in the Rouge River. The northern Trenton
Channel had very high levels of chromium, mercury, nickel and zinc.
Level of most metals in sediments at the Huron River mouth were low rela-
tive to the other stations in the study area. Huron River manganese
levels, however, were far higher than elsewhere.
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ORGANIC CONTAMINANTS
Polynuclear Aromatic Hydrocarbons (PAHs)
Total PAH values range from a low value of 620 ug/kg (ppb) in the Huron
River to an area-wide high of 125,200 ug/kg in the lower Rouge River. The
highest levels of total PAHs were found along the Detroit City riverfront
and in the lower Rouge River. The greatest concentrations of hazardous
PAHs were found in the lower Rouge River and in the main stem of the Detroit
River below Belle Isle. Possible sources are the local steel industry and
Detroit CSOs.
Polychlorinated Biphenyls (PCBs)
The highest concentrations of total PCBs were found near Belle Isle (9,897
ug/kg), below the mouth of the Rouge River (9,726 ug/kg), and in the
Trenton Channel (13,870 ug/kg). The Aroclors PCB 1248 and PCB 1254 pre-
dominated. USEPA Sediment Guidelines for total PCBs were exceeded at three
stations in the northern Trenton Channel .
DDT and Metabolities
The highest levels of total DDT and its metabolities were found at Belle
Isle, (2,265 ug/kg) and were dominated by ODD. High levels of unmetabo-
lized DDT were found at the Rouge River mouth and in the Trenton Channel,
possibly indicating recent additions that have not yet been degraded.
Other Pesticides
Beta-BHC concentrations were elevated at Belle Isle (170 ug/kg), above the
Ecorse River (195 ug/kg) and below the Ecorse River (160 ug/kg). Gamma-
Chlordane was found throughout the study area with peaks at Conners Creek
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(145 ug/kg) and in the Fcorse River (149 ug/kg). Concentrations of other
pesticides did not show regular patterns.
Volatile Drganics
Dichloromethane, trichl oroethene, methyl benzene, ethyl benzene and dimethyl
benzenes were widely present throughout the study area. Their high back-
ground levels nay indicate upstream sources. Peak concentrations of these
volatile substances were found in the Rouge River area, and down river, in-
dicating probable sources in these areas such as Detroit CSOs and local
steel and chemical industry.
Phenol and Phenolics
Concentrations of phenol and other phenolics ranged widely from zero to a
high value of 25,100 ug/kg for 2,4 dimethyl phenol in the northern Trenton
Channel.
Substituted Benzenes and Substituted Cyclic Ketones
Hexachlorobenzene (HCB) is widely present throughout the study area, im-
plying upstream sources. Highest levels of HCR (106 ug/kg) and other
benzenes and cyclic ketones were found in the Trenton Channel.
Other Polycyclic Aromatics and Phthalate Esters
Dibenzofuran concentrations are high below downtown Detroit (3,620 ug/kg)
and in the lower Rouge River (1,910 ug/kg). Peaks for di-n-butyl phthalate
(5,fi90 ug/kg) and Bis (2-ethyl hexyl) phthalate (47,000 ug/kg) are found in
Conners Creek, the lower Rouge River, and below the Ecorse River.
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CONCLUSIONS
Although Detroit River sediments are generally heavily polluted, three
areas stand out as centers of contamination:
1) Rouge River sediments display high levels of every
contaminant category indicating the proximity of sources.
2) Trenton Channel sediments also had high contaminant levels
in all categories, indicating proximity of sources, or
deposition of sediments contaminanted by upstream sources.
3) Conners Creek sediments had high levels of conventional
pollutants, metals and several categories of organic con-
taminants: (i.e., PAH, DDT, PCBs, pesticides, phthalates).
Conners Creek is thus a major source of contamination to
the Detroit River.
In contrast, sediments in both the northern Detroit River near Belle Isle
and in the Huron River had low to moderate contaminant levels.
Sources
It is unclear at this point what the relative impacts are from the many
potential sources of contamination. Ambient, or background and historical
levels of the various contaminants must be known before the load entering
the Detroit River can be determined. Several contaminants, including
volatile organics, HCB, and PCBs seem to have major upstream sources, per-
haps in Lake St. Clair, or the St. Clair River.
The many industrial and municipal point sources clearly have strong impacts
upon sediment quality. The City of Detroit Wastewater Treatment Plant and
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combined sewer overflows, and local steel and chemical industry and oil
refineries are implicated as major contaminant sources. It is presently
unclear whether most sediment contamination results from on-going discharges,
historical discharges, or some combination of the two.
The effects of non-point sources, such as runoff and groundwater seepage to
the river are even more difficult to evaluate. This would require a sy-
stematic study involving an inventory of these sources and monitoring of
their releases.
Interpretation
Knowledge of sediment particle size and total organic carbon (TOC) content
are essential for an understanding of solid state contaminant transport and
estimation of releases to the water column. Normalization of sediment
chemistry data by comparison to TOC, particle size, or conservative metals,
such as aluminum or silicon, would enable one to interpret degrees of pollu-
tion of sediment in inhomogeneous substrates, based upon absolute chemical
concentrations alone.
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INTRODUCTION
This report evaluates sediment chemistry data from the Detroit River and
its three major U.S. qtrihutaries; the Rouge River, the Ecorse River, and
the Huron River. The sediment samples were collected October 26, through
October 28, 1982 by Great Lakes National Program Office staff as part of
its Harbor Sediment Program.
Harbor Sediment Program
Toxic substances are being introduced into the environment from many
sources. Secondary compounds from these toxicants are often found in the
environment. Some of these secondary compounds are more hazardous than the
primary chemicals from which they came.
Sediments serve as a sink, as well as a potential source for toxic and con-
ventional pollutants. Even if discharges of pollutants were completely
eliminated, contaminated sediments could serve as a source of pollution to
the Great Lakes, to aquatic life, and to the populations using the water
supplies for many years to come. Sediments typically concentrate contamin-
ants to many times their concentration in water or effluents because of the
adsorptive properties of fine particles. Sediments can, therefore, serve
as an early warning for the particular contaminants to be looked for in
effluents, waste disposal or treatment lagoons, etc. If one names the
toxic substances Areas of Concern around the Great Lakes, the "problem" is
invariably linked with toxic substances in the sediments: Waukegan Harbor,
Illinois; Indiana Harbor Canal/Grand Calumet River, Indiana; Ashtabula
River, Ohio; Saginaw River and Bay, and the Titabawasee River, Michigan;
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Sheboygan River, Green Bay, and Milwaukee Estuary, Wisconsin; Hamilton Har-
bor, Ontario; and the Buffalo and Niagara Rivers, New York.
The problem of assessing the sources of contaminants in Great Lakes Harbors
is complicated because these harbors are often located at ributary mouths.
The concentrations and distributions of toxic substances in the sediments
reflect upstream contributions, as well as local industrial and municipal
activity. Discharge of contaminated groundwater into surface waters is
gaining recognition as a potentially significant source of sediment contami-
nation. (Swain, 1985).
Some 10 million cubic meters of sediments are dredged annually to maintain
navigation in Great Lakes' ports. Many of these ports contain sediment
that is heavily contaminated with toxic substances. Environmentally safe
dredging and disposal practices are necessary to protect the lakes, wild-
life, and the public while maintaining the economic viability of waterborne
commerce.
"In-Place" pollutants in the sediments have only recently been recognized
as a major source of ecosystem degradation. Also, the analytical capa-
bility to allow meaningful analysis of sediments for toxic organic
substances has improved significantly in recent years. This has resulted in
a limited historical database for organic contaminant levels in sediments.
To fill this void, GLNPO is implementing a multiyear effort to determine
the degree of contamination of Great Lakes' river and harbor sediments by
toxic substances. Sampling priorities are determined by examining fish
flesh contaminant data, locations of likely industrial sources, and by
review of USEPA and other agency data.
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Nineteen surveys were completed in 1981, including a survey of the Buffalo
River and the Niagara River. Ten surveys of Lake Erie harbors were com-
pleted in 1982, including surveys of the Cuyahoga River and Cleveland Harbor,
and the Maumee River. This report summarizes the results from the 1982 survey
of the Detroit River, Rouge River and Huron River, Michigan.
The information generated by this program will be used in making regulatory
decisions on dredging and disposal. It will also help identify environ-
mental "hotspots" requiring further remedial activity, including identifica-
tion and control of sources. The chemicals monitored in the sediments will
form a new information base for the Great Lakes. The GLNPO sediment data
base may be the largest collection of sediment contaminant data in the
United States that is based on consistent sampling and analytical methodology
(Palmer, 1985).
SAMPLING METHODOLOGY
Sediment samples were collected in the manner described in the Methods
Manual for Bottom Sediment Sample Collection (Palmer, 1985). This manual
provides detailed procedures for survey planning, sample collection and
handling, document preparation and quality assurance for sediment sampling
surveys.
Each site survey was designated by determining and plotting, on a large
scale map, the location of sewage treatment plant discharges, combined
sewer discharges (particularly those carrying industrial waste), industrial
discharges, and any other feature that may give rise to contaminated sedi-
ments. To this were added any data on sedimentation patterns that may exist
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from dredging records, and existing data on sediment quality. Supplementary
information, for example, locations of areas of suspected contaminated ground
water discharge, was used to help site sampling locations when available.
All the above information was used to identify locations where contaminated
sediments were most likely to be found. Since sample sites were chosen to
find worst-case conditions, the analytical data do not represent the ambient
sediment contaminant levels in the area. Site locations were determined in
the field by triangulations to easily identifiable landmarks. The derived
locations were then plotted on large-scale charts to determine latitude and
longitude.
In general, sediments will deposit along the edges of a navigation channel,
on the inside edge of a bend of a river, and on the down-drift side of the
littoral drift beach zone. Samples were, therefore, generally collected in
these areas rather than mid-channel. Sounding charts were extremely helpful
for sample site selection since they show the areas requiring the most
dredging and, therefore, areas where the shoal material is depositing. Areas
most likely to show the pollutional effects of man's activity were sampled.
Therefore, when applicable, sample sites were located in the vicinity of
marinas, loading docks, and industrial or municipal outfalls.
SAMPLING EQUIPMENT
Grab samples were retrieved using a Ponar grab sampler. Core samples were
taken using a Wildco brass corer, with a two foot long core tube having a 2"
inner diameter, and a clear Lexan® plastic liner tube. The sediments were
stored at 4°C. Grab samples were homogenized in a stainless steel tub prior
to placement into one quart glass jars. Cores were extruded into a stain-
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less steel tub, and the surficial portions of cores were homogenized prior to
placement into one quart glass jars. A more detailed discussion of sampling
methodology is available in "Methods Manual for Bottom Sediment Sample Collec-
tion," (Palmer, 1985).
ANALYTICAL METHODOLOGY
Prior to non-volatile organic analysis, the sediment samples were allowed to
thaw to 15-25°C. Each sample was manually mixed and allowed to air dry. All
samples were ground with a mortar and pestle. Any sample requiring further
homogenation, at the analyst's discretion, was then passed through a 20 mesh
polypropylene sieve. The percentage of solids of the sample was determined
from a separate aliquot dried at 103-105°C.
Organic Contaminants
Samples were scanned for organic contaminants using gas chromatography tech-
niques. Gas chromatography mass spectrometer (GC/MS) organic scans involve
acid, base and neutral extractions of volatile and semi-volatile priority
pollutants. Electron capture gas chromatographic analysis is the preferred
method for quantitative determination of pesticides and PCBs. Detection
limits for particular compounds vary from one sample to the next due to
matrix effects presented by other compounds contained in the sample. Tables
1 and 2 list organic pollutants scanned for and their detection limits.
Metals
Total mercury concentrations were determined by first digesting the sediment
samples in a mixture of concentrated nitric and sulfuric acid, then analyzing
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the acid extracts using USEPA cold vapor atomic absorption spectrometry
methods. A scan for 24 additional metals was made using Inductively Coupled
Argon Plasma (ICAP) techniques. Table 3 lists the analyzed metals and their
detection limits. All metals values are reported as mg/kg dry weight.
The following eight analyses of conventional pollutants were also run on all
sediments:
Chemical Oxygen Demand (COD)
COD was determined based on a catalyzed reaction with potassium dichromate.
A homogenized, acidified wet sediment sample was mixed with standardized
potassium dichromate, silver sulfate-sulfuric acid and mercuric oxide, and
was refluxed for 2 hours. The COD of the sample is proportional to the
amount of dichromate chemically reduced during the procedure. COD values are
reported as mg/kg.
Oil and Grease
The acidified sediment is dried with magnesium sulfate monohydrate and
extracted with freon in a soxhlet apparatus for four hours. This method is
applicable to the measurement of freon extractable matter from sediments
which contain relatively non-volatile hydrocarbons, vegebable oils, animal
fats, soaps, waxes, greases and related compounds. This method is not
applicable to the measurement of light hydrocarbons that volatilize at
temparatures below 70°C. Petroleum fuels from gasoline through #2 fuel oil
are completely, or substantially lost in the solvent extraction process. Oil
and grease values are reported as mg Freon Extractables/kg dry sediment.
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Cyanide
Cyanide was converted to HCN by means of a reflux-distillation catalyzed by
copper chloride which decomposes metallic cyanide complexes. Cyanide was
determined spectrophotometrically as the cyanide is absorbed in a 0.2 N NaOH
solution. Cyanide concentrations are reported as mg CN/kg dry sediment.
Total Phosphorus
Phosphorus was determined using a Technicon II Auto Analyzer after block di-
gestion of the sample. A 0.5 g dry weight sample was suspended in an HgO-
K204-H2S04 solution and digested at 200°C for 1 hour. Phosphate in the
digestate was quantified using the Automated Ascorbic Acid procedure.
Phosphorus concentrations were reported as mg/kg dry sediment.
Solids
A known weight of homogenized, moist sediment was dried at 105°C. The
total solids were calculated as: % Solids = dry weight g x (100%).
wet weight g
Volatile Solids
Volatile solids were determined by igniting the residue from the total
solids determination at 550°C to a constant weight. Volatile solids were
expressed as a percentage of the total solids in the sample.
Total Kjeldahl Nitrogen (TKN)
TKN was determined on the HgO-K2S04-H2S04 sediment digest analyzed for total
phosphorus. Nitrogen was quantified as ammonia using the alkaline phenol
hypochlorite procedure. Values are reported as mg TKN-N/kg dry weight.
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Ammonia
Alkaline phenol and hypochlorite react with ammonia in the presence of
sodium nitroprusside to form indophenol blue. The intensity of the blue
color is proportional to the concentration of ammonia. Ammonia concentra-
tions are reported as mg N/kg dry sediment.
Quality Assurance
Quality assurance procedures set variance limits for reference samples,
sample splits, and spike samples. Any results obtained outside USEPA accep-
tance limits were flagged as out-of-control, and the samples rerun.
More detailed descriptions of the methodology for sediment analysis and
quality assurance are available in the Upper Great Lakes Connecting Channels
(UGLCC) Work/Quality Assurance Plan for: 1982 Detroit, Michigan Area Sedi-
ment Survey and in Appendix B of this report.
THE SETTING
Urban and Industrial Development
The Detroit River, one of the busiest commercial waterways in the world,
flows thirty-two miles southeast from Lake St. Clair, past an area of
intense urban and industrial development, to Lake Erie. The IJC has class-
ified the river as an Area of Concern due to degraded water and sediment
quality, primarily along the west bank below the Rouge River mouth. Steel,
auto, and chemical industries are concentrated on the banks of the river and
its tributaries, and utilize the waters for cooling and processing water.
(Figure 1, Detroit area industry). The Detroit Rivers major tributary, the
Rouge River, is also classified as an IJC Area of Concern primarily due to
contaminated sediments (IJC, 1985).
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Geology and Hydrogeology
Glacial drift, ranging in thickness from zero to over three hundred feet is
the dominant surficial geological material in the Detroit area. The drift
is underlain by bedrock of Early Mississippian to Early Devonian age, dip-
ping gradually to the north and west. Rocks of the Devonian Detroit River
Group and the Silurian Salina formation outcrop in the lower reaches of the
Detroit River in Trenton, and on Grosse lie. Glacial deposits, for the
most part, are poorly sorted fine materials consisting mostly of lacustrine
and morainal deposits and till plains, having low hydraulic conductivites.
Distribution of the glacially-derived materials is non-homogeneous, however.
Patches of beach sand and coarse-grained outwash deposits with high hydraulic
conductivities are found scattered throughout the area. Other coarse-
grained deposits, originating during pre-glacial conditions, or water-
sorted deposits from earlier stages of glaciation in some areas underlie the
most recent glacial materials, and are often good groundwater reservoirs.
Coarse alluvial sediments, resulting from the pre-glacial drainage system,
lie below Highland Park and Hamtramck, and extend out to Belle Isle (Figure
2, Bedrock Surface Topography). Such deposits may be important pathways for
contaminant transport to Detroit River sediments. An area-wide groundwater
study is necessary to determine the impacts of groundwater seepage upon the
river sediments and the Detroit River as a whole.
Hydrology
Mean Detroit River discharge, from 1900 to 1978, is roughly 184,000 cfs (G.L.
Water Levels Facts, 1984). The river falls about three feet from Lake St.
Clair to Lake Erie, and average velocities vary from one to over two feet per
second. Water depths and flow are dependent upon Lake St. Clair and Lake
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Erie levels which fluctuate seasonally. Superimposed upon the seasonal
fluctuation are storm-related short-term variations, which affect and may at
times, even reverse the Detroit River flow ( Figure 3, Detroit River study
area).
The Detroit River has two well-defined reaches having distinct hydraulic
characteristics. The upper stretch of the river, from Lake St. Clair to just
above Fighting Island (above the Ecorse River) is a broad bend about thirteeen
miles long flowing as a single channel 2,000 to 3,000 feet wide. The river
is 30-50 feet deep mid-channel. Its narrowest section is at the Ambassador
Bridge where it is 1900 feet wide. Maximum mid-channel velocities here
approach four feet per second.
In the lower reaches, the river is one mile to two miles wide, and shallow.
The flow here is considerably slower requiring continuous dredging. The
river is divided by islands into several major channels. Depths are maintained
at twenty-seven to twenty-eight feet by dredging. The Trenton Channel is a
second major channel about one thousand feet wide between Grosse Isle and the
Michigan mainland. Navigation depths are maintained at twenty-seven and
twenty-one feet in the northern portion of the Trenton Channel, while natural,
undredged depths at the southern end are less than ten feet (Station DTR82-
45, and below). Rocks of the Detroit River Group outcrop in the lower reaches,
and shipping channels have been cut through this exposed bedrock to a depth
of thirty feet.
Flow information for the Detroit River and flow hydrographs for the Rouge and
Huron Rivers indicate that the sampling period in late October is typically a
time of relatively low flow (Figure 4, Hydrographs) implying net accretion of
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sediments, including some fine sediments. Similarly, Manuscripts for the 1982
Water Year indicate that October 1982 was a period of baseflow for the tribu-
taries (USGS, 1983). Therefore the influence of groundwater discharge upon
the streams, especially the Rouge River, was at a maximum at this time. Also,
during periods of low flow, Detroit River water and sediments are carried up
the Michigan tributaries, especially when winds are out of the east.
Mineralogy
A. Mudroch (1984), using non-quantitative powder x-ray diffraction techniques,
found the mineralogy of the Detroit River sediments to be composed primarily
of calcite and dolomite, quartz, feldspars and the clay minerals; illite,
chlorite and kaolinite. Quartz and calcite comprise the >63 urn, or sand size
category. Dolomite and the feldspars largely made up the 4-63 urn, or silt-
sized category. Illite, chlorite, kaolinite and "other" minerals made up the
<4 urn, or clay-sized category.
RESULTS AND DISCUSSION
Sampling Sites and Reporting
Sediment grab samples were collected at sixty-five locations along the western
bank of the Detroit River and three of its tributaries: the Rouge River, the
Ecorse River, and the Huron River from October 26 to October 28, 1982 (Figure
5, USEPA Detroit 1982 Sediment Sampling Sites; Figure 6, Huron River Michigan
Sediment Sampling Sites). In tables and figures throughout this report, sedi-
ment stations will be listed in a downstream order for easy geographical
correlation. Although some of the parametric data displayed in histograms
appears to be grouped in some way, the histograms are not intended to imply
any kind of continuity from one sample to the next. Sediment data is rather
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patchy by nature. To further ease comparisons and correlations, the study
area has been divided into eight sub-areas, each having rather distinct hydro-
logical and cultural characteristics:
BELLE ISLE (Stations DTR82-01, DTR82-03, DTR82-05A)
Belle Isle itself is a recreational area, The channel west of the island is
characterized by extensive shoal areas. Loading docks, marinas, light industry,
a major tire company and a coal-fired power plant are located along the Michigan
mainland. Conners Creek (DTR82-03) is below a major automobile assembly plant,
and below a major structure of the City of Detroit Combined Sewer system, the
Conners Creek Backwater Gate. (Figure 7, Detroit area CSOs).
DOWNTOWN DETROIT (Stations DTR82-08, DTR82-13)
This sub-area extends from the south end of Belle Isle, past downtown Detroit
to the Ambassador Bridge. Land use along the shore of this fast flowing,
narrow portion of the river is characterized by light industry and commercial/
residential uses. Over thirty Detroit Combined Sewer Overflow (CSO) points are
located along the Detroit River in this sub-area.
ROUGE RIVER (Stations DTR82-19, ROR82-07, ROR82-06, ROR82-02)
The Rouge River sub-area includes the Detroit River between the Rouge Old Chan-
nel and the Rouge Short-cut Canal, and the Rouge River itself below the Ford
Dearborn plant. The entire area is heavily developed with automobile assembly,
steel, paper and pulp, and oil refining industry. In addition, the Detroit
waste water treatment plant (WWTP) and 180 CSOs discharge to the Rouge River.
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ROUGE RIVER to ECORSE RIVER (Stations DTR82-22, DTR82-23, DTR82-25, DTR82-26,
DTR82-27)
The portion of the Detroit River between the Rouge River mouth and the Ecorse
River mouth is a transitional area where the river changes from a narrow fast-
flowing channel to a broad channel divided by islands. It is characterized by
heavy steel manufacturing and oil refining industry.
ECORSE RIVER (Stations DTR82-52, DTR82-53, DTR82-29, DTR82-30)
The north and south branches of the Ecorse River and the portion of the Detroit
River immediately downstream of the Ecorse River mouth comprise this sub-area.
Heavy steel manufacturing and chemical industry which discharges to the Detroit
River are the major land uses. Fighting Island, Mud Island, Grassy Island and
the northernmost point of Grosse lie have been used for disposal of industrial
waste and dredged material .
NORTHERN TRENTON CHANNEL (Stations DTR82-32, DTR82-38, DTR82-56, DTR82-49)
The northern portion of the Trenton Channel is dredged to a depth of twenty-
seven feet to accommodate large ships. Chemical industry and residential areas
characterize the mainland land use in the extreme northern portion of the
channel above the northern tip of Grosse Isle. Heavy steel and chemical manu-
facturing is the characteristic land use below the town of Wyandotte. Hunting-
ton/Monguogon Creek drains a heavily industrialized area containing landfills
into the Trenton Channel at station DTR82-38. Grosse lie itself is largely
residential, except the northern tip, which is a former waste disposal area.
SOUTHERN TRENTON CHANNEL (Stations DTR82-43, DTR82-45, DTR82-48)
The southern Trenton Channel is shallow and undredged. Although it is generally
an industrial area, characterized by power, steel and chemical industry, the
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level of industrial activity is less than that in the northern Trenton Channel.
Several small tributaries drain into the southern Trenton Channel. Extensive
shallow sediment depositional areas are found at the southern end of Hrosse
Isle.
HURON RIVER (Stations HDRR2-01, HDRR2-0?, DTRR2-57)
This sub-area is comprised of the downstream reach and mouth of the Huron
Piver. The river mouth and the surrounding wetlands comprise the Pointe Mouilee
State Game Area. A confined disposal facility is under construction at the
mouth of the river. Upstream sources of contamination on the Detroit River may
impact this area when westerly winds on the Detroit River and Lake Erie move
contaminated water and sediments upstream. In addition9 the Huron River drains
with potential municipal and rural sources of contamination.
Field Observation. (Table 4, Field Observations)
Field observations indicate sediment from about half of the stations contained
sand or coarser-grained materials. Sediment from ten of twenty-eight stations
was said to contain "muck" or "ooze", indicating input of recent and organic
material. Rravel was observed in two stations in the study area below the
Ecorse River mouth, and in the Huron River, perhaps indicating an energetic
flow regime. An oily sheen, or an oily or chemical odor was observed in
eleven of twenty-eight samples and in stations from all the sub-areas with the
exception of the Huron River area.
CONVENTIONAL POLLUTANTS
Conventional pollutant levels (total volatile solids, oil and grease, COD, TKN,
ammonia, phosphorus and cyanide) indicate severe sediment contamination
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throughout most of the study area. Sampling sites near Belle Isle to the
north, and in the Huron River to the south, have less extreme contaminant
levels. The Rouge River sediments stand out as the most contaminated by
conventional pollutants: the very highest levels in the study area of total
volatile solids, COD, TKN, ammonia and cyanide are all found in one sample up-
stream on the Rouge River (ROR8P-D7). The highest levels of phosphorus and oil
and grease are found in sediments from the central portion of the Trenton Chan-
nel (Table 5, Conventional Pollutants).
Total Volatile Solids. Total volatile solids levels are high throughout most
of the study area, and range from 2.4% to 23.4%. The IISEPA Sediment Guidelines
for the "heavily polluted" categories were exceeded in 71% of the samples, 14%
are moderately polluted and 14% are "unpolluted." The mean % total volatile
solids level is 9.53%, and falls in the "heavily polluted" category. Highest
levels are found in the Rouge River sub-area. (Figure R, %Total Volatile
Solids.)
Oi1 and Grease
Determinations of oil and grease levels were performed as supplemental analyses
in ]98B. Only eighteen of the samples had sufficient material for analysis.
Of these eighteeen, sixteen, or 89% exceeded US EPA Sediment Guidelines for the
the "heavily polluted" category. The remaining two sites, in the Huron River
subarea, had "moderately polluted" oil and grease levels. The range in values
values was very broad, from 1,75? mg/kg to 38,990 mg/kg. The mean oil and
grease level is lfi,??5 mg/kg, falling well into the "heavily polluted" category.
The highest levels were found in the northern Trenton Channel, in Connors Creek,
above the Ecorse River mouth and in the Rouge River (Figure 9, Oil and Grease).
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Chemical Oxygen Demand. COD levels are high throughout most of the study area,
ranging from 31,000 mg/kg to 300,000 mg/kg. IISEPA Sediment Guidelines for
"heavily polluted" are exceeded in 75% of the samples, 18% are moderately pol-
luted, and 7% are "unpolluted." The mean COD level of the study is 142,000
mg/kg and falls in the "heavily polluted" category. Highest levels are found
in the Rouge River and the northern Trenton Channel sub-areas (Figure 10, COD).
Total Kjeldahl Nitrogen. TKN levels are high in many of the study area sedi-
ment samples, and range from 640 mg/kg to 8600 mg/kg. 54% of the samples have
TKN levels which exceed USEPA Sediment Guidelines for "heavily polluted," 35%
are moderately polluted, and 10% are "unpolluted." The mean TKN level in the
study area is 247? mg/kg and falls in the "heavily polluted" category. The
highest TKN level is found in the Rouge River (Figure 11, TKN).
Ammonia. Ammonia levels are very high in most of the study area, and range
from 50 mg/kg to 1400 mg/kg. 57% of the samples exceed IISEPA Sediment Guide-
lines for "heavily polluted," 25% are "moderately polluted" and 18% of the
samples are "unpolluted." The mean ammonia level in the study area is 365
mg/kg, which is in the "heavily polluted" category. The highest ammonia levels
were found in the Rouge River, and downstream in the area between the Rouge and
Fcorse Rivers, perhaps indicating a major source in the Rouge River (Figure 12,
Ammonia).
Phosphorus. Phosphorus levels are very high throughout most of the study area,
exceeding IISEPA Sediment Guidelines for "heavily polluted" in 86% of the sam-
ples. 7% of the sediment samples are "moderately polluted," and another 7% are
"unpolluted." The mean phosphorus level of 2604 mg/kg falls in the "heavily
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polluted" category. Phosphorus values range from 350 trig/ kg to 6700 mg/kg, and
the highest levels are found above the Ecorse River mouth and in the Trenton
Channel (Figure 13, Phosphorus).
Cyanide. Cyanide levels are very high throughout most of the study area rang-
ing from 0.] ng/kg to 33.0 mg/kg. IISEPA Sediment Guidelines for "heavily
polluted" were exceeded in 71% of the samples. The mean cyanide level over the
whole study area is B.85 mg/kg, and falls in the "heavily polluted" category.
Peak levels are seen in Conners Creek, in the Rouge River, above the Ecorse
River mouth, and in the northern Trenton Channel. Detection levels for cyanide
exceed the "heavily polluted" category, therefore, caution should be excerised
in interpreting these data (Figure 14, Cyanide).
DISCUSSION
Figures 8-14 illustrate clearly that all the sub-areas with the exception of
the Ecorse River and the Huron River are heavily polluted. Furthermore, three
sub-areas seem to be exceptionally polluted: the Rouge River, the area between
the Rouge and the Ecorse River mouths, and the northern Trenton Channel. The
largest concentrations of heavy industry in the study area are found in these
sub-areas. The large number of CSOs in the Rouge River undoubtedly affect con-
ventional pollutant levels there. The anomalously high levels of conventional
pollutants in Conners Creek relative to the other Belle Isle area stations in-
dicate the influence of the automobile assembly plant and Detroit CSO's upon
sediment quality. The levels of all the individual conventional pollutants,
averaged over the whole study area, fall in the "heavily polluted" category.
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METALS
The levels of heavy metal s, for which HSFPA Sediment Guidelines have been set,
indicate that metals contamination of sediments in the Detroit area is both
severe and wide-spread. Mean levels for all ten of these metals (cadmium,
chromium, mercury, nickel, zinc, cooper, barium, iron, lead and maganese) ex-
ceed the IISEPA Sediment Guidelines for "heavily polluted." Metals contami-
nation is less significant in two sub-areas: two stations in the Belle Isle
area, and three stations in the Huron River area have low to moderate metals
contamination levels (Table 6, Metals).
Lead. Lead levels are very high throughout most of the study area, and range
from 21.n mg/kg to 81 n mg/kg. IISEPA Sediment Guidelines for "heavily polluted"
are exceeded in 89% of the samples. 7% are "moderately polluted", and only 4%
are unpolluted. The mean lead level is 335 mg/kg, and falls in the heavily
polluted category. The highest lead levels are found near Belle Isle in Conners
Creek, in the Rouge River, in the Ecorse River, and in the northern Trenton
Channel (Figure IB, Lead).
Zinc. Zinc levels are high throughout most the study area, and range from 76
mg/kg to 35Dn mg/kg. US EPA Sediment Guidelines for the "heavily polluted"
category are exceeded in 82% of the samples, 14% are "moderately polluted,"
and 4% are "unpolluted." The mean zinc level is 891 mg/kg, and falls in the
"heavily polluted" category. The highest zinc levels are found in the Belle
Isle area in Conners Creek, in the Rouge River area, and in the northern Tren-
ton Channel (Figure Ifi, Zinc).
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Iron. Iron levels are high throughout most of the study area, and tiSEPA
Sediment Guidelines for "heavily polluted" are exceeded in 68% of the samples.
18% are "moderately polluted" and 14% are "unpolluted." Iron levels range
from 10,000 mg/kg to 89,000 mg/kg, and the mean level is 38,392 mg/kg falling
in the "heavily polluted" category. Highest levels are found in the Rouge
River area, in the area between the Rouge and Ecorse River mouths, and
in the Trenton Channel , thus implicating the local steel industry as a
source of this contamination (Figure 17, Iron).
Nickel. Nickel levels are high throughout most of the study area and range
from 15 mg/kg to 300 mg/kg. The USEPA Sediment Guidelines for the "heavily
polluted" category are exceeded in 68% of the samples, 25% are "moderately pol-
luted," and 7% are "unpolluted." The mean nickel level is 105.7 mg/kg, and
falls in the "heavily polluted" category. Highest levels are found in the
Rouge River area, between the Rouge and Ecorse River mouths, and in the
northern Trenton Channel; a distribution very much like the iron levels in
Detroit area sediments (Figure 18, Nickel).
Manganese. Manganese levels are high throughout most of the study area. USEPA
Sediment Guidelines for the "heavily polluted" category are exceeded in 71% of
the Detroit samples, 18% are "moderately polluted", and 11% are "unpolluted."
The mean sediment manganese level is 750 mg/kg, and falls in the "heavily
polluted" category. Manganese levels range widely, from a low of 160 mg/kg in
the Belle Isle area to a high of 2800 mg/kg in the Huron River sediments
(Figure 19, Manganese). The high manganese level in the Huron River sediments
may reflect the high high oxidation state of sandy sediments at this site.
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Cadmium. Cadmium levels are rather high in a large part of the study area.
USEPA Sediment Guidelines for "heavily polluted" are exceeded in 57% of the
samples, and 43% are "unpolluted." The mean cadmium level in the sediments is
11.1 mg/kg, and falls in the "heavily polluted" category. Values range from
0.2 mg/kg to a high of 96 mg/kg in the Rouge River. Cadmium levels are consis-
tently high in the Trenton Channel. (Figure 20, Cadmium).
Chromium. Chromium levels are very high throughout most of the study area.
USEPA Sediment Guidelines for the "heavily polluted" category are exceeded in
71% of the study area sediment samples. 14% are "moderately polluted," and 14%
are "unpolluted." The range in values is from 9.8 mg/kg in Huron River sedi-
ments to a high of 680 mg/kg in the northern Trenton Channel. The highest
levels are found in the Rouge River, between the Rouge and Ecorse River mouths,
and in the northern Trenton Channel, again implicating the local steel industry
as a source (Figure 21, Chromium).
Bariurn. Barium levels are very high throughout almost the entire study area,
and range from a low of 36 mg/kg to a high of 500 mg/kg. USEPA Sediment Guide-
lines for "heavily polluted" are exceeded in 93% of the samples, and the
remaining 7% are "moderately polluted." The mean barium level of 194.5 mg/kg
is well above the "heavily polluted" level. Peak barium levels are found in
the Belle Isle area in Conners Creek, in the Rouge River, between the Rouge and
and the Ecorse River mouths, and in the northern Trenton Channel (Figure 22,
Barium).
Copper. Copper levels are high throughout most of the study area, and range
widely, from 17 mg/kg in the Huron River to a high of 720 mg/kg in the Rouge
River. USEPA Sediment Guidelines for "heavily polluted" are exceeded in 79% of
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the samples, 14% are "moderately polluted," and 7% are "unpolluted." The mean
copper level is 15Q rig/kg, and falls in the "heavily polluted" category.
Copper level peaks are found in the Rouge River, above the Ecorse mouth, and in
the northern Trenton Channel, again implicating the local steel industry as a
major source. (Figure 23, Copper).
Mercury. Mercury levels are high in much of the study area sediments. Values
range from a low of 0.? mg/kg in the Huron River to a high of 3.6 mg/kg in the
northern Trenton Channel. USEPA Sediment Guidelines for "polluted" are exceeded
in $?% of the samples, rendering sediments from these areas unsuitable for open
lake disposal, regardless of what other data indicate. The mean mercury level
of l.lfi mg/kg falls in the "polluted" category. Peak values are found in the
Trenton Channel and the Rouge River, thus implicating the local steel and chem-
ical industry as sources of contamination. (Figure 24, Mercury).
DISCUSSION
Figures 15 - 24 indicate widespread, high level contamination of sediments by
the metals for which Sediment Guidelines have been set. The highest levels for
the individual metals define four problem areas: the most serious contamination
is seen in the Rouge River area. The area between the Rouge and Ecorse Rivers,
Conners Creek in the Belle Isle area, and the Trenton Channel also have signi-
ficant metals contamination problems.
Levels of the other trace metals follow roughly the same trends as the metals
for which USEPA Sediment Guidelines have been set. (Table 7, Trace Metals,
Figures 25-33). It appears that local steel and chemical industry and perhaps
the Detroit CSOs are responsible for the elevated levels of trace metals in the
study area.
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Levels of the major metals (Ca, K, Mg, NA and Al) are a function of particle
size and mineralogy. Ca and Mg levels are attributable to dolomite particles in
the sediment. K and Al originate with the dominant clay mineral illite. Na is
derived from sodic, feldspathic rocks, but other sources (chemical industry,
road salt) may have localized effects. (Table 8, Figures 34-37, Major Metals)
(Tables Q, Hetal s Summary).
A. Mudroch (1984) analyzed the metals content of the individual size fractions
of Detroit sediments, and found that the heavy metals correlate well with the
fine size fraction: Zn, Ni, Cr, and Pb were found in both the <13 urn and the
48-63um fractions. Our field observations confirm the close relationship bet-
ween metals and particle size: all of the highest metals values were found in
samples composed predominantely of fine materials (Table 4, Field Observations).
Therefore, to derive meaningful interpretations of sediment metals analyses,
one needs accurate particle-size information.
Most metals are present in soil and natural sediments in significant concentra-
tions, and even trace metals are naturally present to some degree. It is
important, therefore, to be able to distinguish between constituents derived
from natural, or ambient conditions, such as erosion or weathering of natural
materials, and anthropogenic inputs. Several methods to normalize sediment
metals data are presently in use, including comparison to silicon levels, alum-
inum levels, or particle size. While such normalization may yield meaningful
information, this report merely presents metals levels as they were found.
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ORGANIC CONTAMINANTS
Hydrophobic organic substances are rather easily adsorbed from aqueous solu-
tions onto available surfaces, the amount adsorbed being dependent upon the
nature of the surface. The adsorption is strongly correlated with the Total
Organic Carbon (TOC) content, and the surface area of the particles, with TOC
dominating over surface area in importance by three to one. In sedimentary
deposits with a high organic content, especially those with significant amounts
of organic solvents, hydrophobic suhstanes can be highly mobile (Griffin &
Chian, 1980).
In the aquatic environment, the fate of hydrophobic organic contaminants in the
absence of nonpolar organic solvents, is strongly linked to sediments as they
are deposited, resuspended, and transported as bedload or suspended load. Two
other transport pathways are available to these compounds once they enter the
aquatic environment: 1) dissolution in water, the magnitude of which is deter-
mined by sediment/water partition coefficients for the individual organic
compounds, or 2) direct ingestion by benthic organisms and bottom feeding
fishes, and nektonic or planktonic organisms in the water column which ingest
suspended sediments. These latter two pathways provide the link with the food
chain.
Polynuclear Aromatic Hydrocarbons (PAHs). Polynuclear aromatic hydrocarbons
(PAHs) are widely recognized components of fossil fuels and of fossil fuel
combustion products. They occur naturally in forest fires, volcanoes, degraded
biological materials, and also in fireplaces, coal furnaces, auto emissions and
incinerators (Eldridge et a!., 1984). Other common sources of PAHs include
steel mill foundry sand, coal-pile runoff, coal-ash leachate, coke, coal-tar
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deposits and urban street runoff. Many PAH compounds are carcinogenic to
humans and thus are on the EPA Priority Pollutants list. Naphthalene is widely
used as a starting material for various dye intermediates and has found some
use as a solvent and lubricant. Other PAHs have very limited or no industrial
significance.
Organisms evolutionarily above the level of insect/invertebrate readily meta-
bolize PAHs, and these metabolites, especially epoxides and diolepoxides, are
believed to be the ultimate carcinogens for PAHs (Toxic Chemicals Issues and
Research Priorities, 1984).
PAHs are hydrophobic organic compounds, and thus readily adsorb onto suspended
particulate matter in an aquatic environment. They have a close association
with the TOC content of soils and sediments. PAHs are associated with fine
particles (<63um), and higher PAH concentrations are evident with increasing
silt/clay content (Griffin & Chian, 1980).
Sources of PAHs. There are many potential sources of PAHs in the Detroit area:
hydrocarbon refineries in Detroit, and upstream in Sarnia, shipping, and spills
of fossil fuels on the Detroit River, steel and coking operations in Michigan,
production of coal tar, and urban runoff from both sides of the river all con-
tribute to the PAH content of the sediments.
Total PAH. Fourteen PAH compounds, ranging from low molecular weight naphtha-
lene to high molecular weight benzo(a)pyrene, have been found in the Detroit
198? Sediment Survey. (Figure 38-47, PAHs). A convenient method to examine
PAH distribution along the river is simply to sum the values for the indivi-
dual compounds and compare total PAH values (Table 10, Summary Table). Total
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PAH values in the study area range from 620 ug/kg on the Huron River to
125,200 ug/kg in the lower Rouge River (ROR82-02). Along the river, locations
of total PAH "hotspots" in the sediments help identify major source areas.
Urban runoff and shipping spills in downtown Detroit, industry and municipal
projects on the Rouge River, the steel industry above the Ecorse River mouth,
and the steel and chemical industry in the Trenton Channel all appear to be
likely sources of PAHs. Overall mean PAH values are lower in the downstream
portions of the Detroit River.
Fossil Fuels Vs. Fossil Fuel Combustion Products. Closer inspection of the
distribution of individual PAH compounds yields additional information which
allows more definitive judgements concerning sources. PAHs derived from fossil
fuels, or non-combustion PAHs, are characteristically of lower molecular weight
(e.g., naphthalene) than high molecular weight PAHs originating from fossil
fuel combustion products (e.g. benzo(a) pyrene). Therefore, compositional pro-
files of PAH distributions provide a useful means of monitoring changes in PAH
content and sources between the sediment stations (Boehm and Farrington, 1984).
The Detroit area PAH compositions are dominated by the heavier 3,4 and 5-ringed
PAHs over the lighter two-ringed naphthalenes. Thus, the overall PAH assemb-
lage is dominated by fossil fuel combustion PAHs indicating either greater
additions of high molecular weight PAHs, or their preferential adsorption by
sediments. (Table 11, PAH). In certain areas along the Detroit River, the
greater dominance of lower molecular weight PAHs over the higher molecular
weight PAHs may indicate differing sources of total PAHs. Dominance by low
molecular weight PAHs is evident at a number of sampling stations: DTR82-01,
_ 31 _
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DTR82-03, DTR82-05A, ROR82-07, ROR82-06, DTR82-52, DTR82-53, HUR82-02, HUR82-01
DTR82-57 (in the Belle Isle, Rouge River, Ecorse River and Huron River areas).
These stations, with the exception of the Rouge River stations, also tended to
have lower than average total PAH values. OTR82-19, near the mouth of the
Rouge River, has a rather singular PAH distribution, having the highest concen-
tration of naphthalene in the study area, coupled with reduced levels of high
molecular weight PAHs, suggesting fossil fuel spills as the major source of
PAHs here. Station DTR82-32, in the Wyandotte Yacht Club, shows the highest
relative amounts of both naphthalene and high molecular weight PAHs. Overall
sediment PAH levels are highest in the Rouge River.
Generally, the important sources seem to be industrial (fossil fuel combustion
products) and municipal (urban runoff) discharges to the Detroit River. Fos-
sil fuel spills are probably locally important sources at DTR82-03, DTR82-19,
ROR8206, ROR82-02, and DTR82-32 (Wyandotte Yacht Club). The absence of high
molecular weight PAHs, and overall low total PAH values found upstream from
Belle Isle, and up from the mouths of tributary streams, indicate that the pre-
dominant sources of PAH are industrial and municipal sources along the Detroit
River.
PAH Hazard Ranking. Distribution of PAHs along the Detroit River was also eval-
uated in terms of a hazard ranking of individual PAH compounds. The mutagenic
and carcinogenic activity of a small number of specific PAH compounds, for
example, benzo(a)pyrene, is well known. However, synergistic and antagonistic
effects between PAH compounds, and uncertainties about carcinogenic and muta-
genic effects of PAH metabolites complicates evaluation of the hazards
associated with PAHs. At best, a first order approximation of hazard can be
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made based on linear combinations of individual PAH values. The six most
hazardous PAHs analyzed for in this study, as per Mil liken et al, are:
benzo(a)pyrene, benz(a)anthracene and chrysene, indeno(l,2,3,c,d)pyrene, benzo-
(b&k)fluoranthene, and phenanthrene. Two methods of estimating the PAH
hazard assocated with sediments were used: 1) summation of the six most
hazardous PAH and, 2) inspection of benzo(a)pyrene values (Tables 12, Hazardous
PAHs).
Inspection of Table 12 shows: 1) hazardous PAHs are pervasive throughout the
study area 2) less, or none of the most hazardous PAH compounds are found in
the tributaries, and upstream from Belle Isle on the Detroit River, 3) the
highest hazardous PAH values are seen at ROR82-02, in the Rouge River, and
DTR82-13 and OTR82-08, near downtown Detroit, indicating sources in urban run-
off or CSOs and industrial sources in the Rouge River.
Thus, we conclude that a few major sources of PAHs impact upon the Detroit
River in the upstream portion. Downstream sources may be continuous, while
transport and deposition of sediments in the lower river effectively homoge-
nizes PAH distribution.
PCBs
Total PCBs Detroit sediments exceed USEPA Sediment Guidelines for total PCBs
(greater than 10 mg/kg) at three stations in the northern Trenton Channel:
DTR82-32, DTR82-38, and DTR82-49. Eighteen stations widely distributed over
the study area had elevated levels of total PCBs (1 to 10 mg/kg). Seven sta-
tions, mainly in the Belle Isle area and upstream on the Huron River, had loi
total PCB levels (less than 1 mg/kg) (Table 13, PCBs).
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Generally, the highest PCB values are found in the areas of heavy industry in
Ecorse, Wayndotte and Riverview on the northern Trenton Channel. However, the
high levels of total PCBs in Conners Creek in the Belle Isle area and in the
downtown Detroit area may implicate Detroit CSOs as major sources to the system.
Although PCB loadings in the study area appear to be high, upstream sources may
also add a significant load upon Detroit River sediments. PCB-tainted sedi-
ments from Saginaw Bay and Lake St. Clair are resuspended by storms, and the
sediment bound-PCBs are entrained in the dynamic fluvial environment of the
Detroit River (Thorn!ey and Hamdy, 1984).
Inspection of the distribution of the Aroclor components of the PCBs may yield
some information about sources of PCBs. The PCB mixtures (Aroclors) which were
analyzed by GC/EC, range from PCB-1242, with 42% chlorination, to PCB-1260,
with 60% chlorination. The less-chlorinated Aroclors are much more soluble in
water than the highly-chlorinated Aroclors which are more hydrophobic. The
highly chlorinated Aroclor 1260, thus, has greater adsorption potential than
the less-chlorinated Aroclor-1242 (Eisenreich et al., 1983). PCB-1242 levels
are generally low, ranging from zero to 956 ug/kg. Significant levels are
found at sites immediately above and below the Ecorse River (Figure 48,
PCB-1242).
The highest levels of the four PCB mixtures are found for PCB-1248 on the
Detroit River, between the Rouge and Ecorse River mouths. PCB-1248 ranges from
zero to 6940 ug/kg. Strong peaks of PCB-1248 are also found at all stations in
the northern Trenton Channel, and in Conners Creek in the Belle Isle area
(Figure 49, PCB-1248).
- 34 -
-------
PCB-1254 levels range from zero to 3638 ug/kg. Peak levels are found in the
northern Trenton Chanel, in the Belle Isle area in Conners Creek, in the
Detroit area, and between the Rouge and Ecorse River mouths (Figure 50, PCB-
1254).
PCB-1260 ranges from zero to 3946 ug/kg. Peak levels are found in the northern
Trenton Channel, on the Detroit River in Downtown Detroit, and between the
Rouge and Ecorse River mouths (Figure 51, PCB-1260).
Generally, PCB levels are highest in the northern Trenton Channel, between the
Rouge and Ecorse River mouths, and in Conners Creek in the Belle Isle area, and
in the northern Detroit River. The Rouge River did not exhibit high levels of
any of the PCB mixtures, nor did either of the other two tributaries to the
Detroit River, or most of the stations on the northern Detroit River. This may
signify the relative importance of the contributions of PCBs from CSOs and the
chemical industry along the Detroit River.
Oliver and Bourbonierre (1984), from comparison of Lake Huron/Lake St. Clair
and Lake Erie sediments, observed that the PCB concentration increases between
Lake Huron/Lake St. Clair and Lake Erie, indicating major sources along the
Detroit River. Also they noted that the degree of chlorination increases sub-
stantially over the same length: the predominant Aroclor in Lake Huron/Lake
St. Clair is PCB-1242 while in western Lake Erie it is PCB-1260. Modelling of
dilution factors led them to conclude that a disproportionately high concen-
tration of Aroclor-1260 is contained in the Detroit River and that the Detroit
River is the major source of PCBs to western Lake Erie. Although a consider-
able amount of PCBs were found by the 1982 Detroit Sediment Survey to be
be entering the river, they tended to be Aroclor-1248 rather than Aroclor-1260.
- 35 -
-------
Summations of the levels of the four PCB mixtures over the whole study area
give an indication of their relative importance in the Detroit sediments.
PCB-1248 comprises almost 43% of the total PCBs, PCB-1254 is 30%, PCB-1260 is
26%, and PCB-1242 accounts for only 1.5%. Thus, overall, PCB-1248 is the dom-
inant PCB mixture observed in the sediments. However, not all the stations
exhibit the same proportions of PCB mixtures (Table 13, PCB).
Inspection of the distribution of Aroclors in the Detroit River sediments shows
that there are three characteristic types of sediments in terms of chlorina-
tion: the majority of the sediment samples were heavily weighted toward
either PCB-1248 or PCB-1260. The rest show approximately equal proportions of
of the various isomers. Furthermore, all the stations exceeding USEPA Sed-
iment Guidelines for total PCBs are highly skewed towards the less chlorinated
Aroclors (PCB-1248). Those samples having total PCB levels in the range
from 1,000 ug/kg to 10,000 ug/kg are skewed either towards PCB-1248, or PCB-
1260. Samples with low total PCB levels represent background levels and
tend to have a more even distribution of the PCB mixtures. Thus, PCB-1248
dominates the sediments having the highest total PCB levels.
This appears to contradict Oliver and Bourbonnierre's conclusions that Detroit
is the major source of PCB-1260 to western Lake Erie. Although a heavy PCB
load enters the Great Lakes at Detroit, these PCBs are of lower % chlorination
than those found in western Lake Erie.
A possible cause of this discrepancy may be subsequent weathering of PCBs by
volatilization and degradation, which would alter the composition of PCB mix-
tures (Armstrong and Swackhammer, 1983). Aroclor-1248 is much more soluble in
- 36 -
-------
water, and thus more susceptible to volatilization out of the system. Also,
lower-chlorinated isomers are more easily degraded by micro-organisms than
higher-chlorinated isomers (Griffin and Chian, 1980). The increase in percen-
tage of chlorination going downstream from Lake Huron/Lake St. Clair to western
Lake Erie may be mostly a function of residence time in the system. Therefore,
use of Aroclor 1260 as a conservative tracer of Detroit inputs is inappropriate.
The effects of residence time upon chlorination of PCBs may indicate a larger
contribution of PCBs to western Lake Erie from sources upstream from Detroit
than were previously suspected.
In Detroit the sediments violating the USEPA Sediments Guidelines which are
relative lower in chlorination, are relatively recent additions to the sedi-
ments. Those with lesser PCB concentrations and having greater degree of
chlorination have spent more time being subjected to volatilization and degrad-
ation in the aquatic system, either in transport from St. Clair River/Lake St.
Clair, or within the Detroit River system. The higher chlorinated isomers are
less soluble in water, preferentially adsorbed by sediments, less degradable
by micro-organisms, and less volatile from water than lower chlorinated isomers
(Griffin and Chian, 1980). The samples showing the low PCB levels represent
ambient conditions and may signify substantial upstream sources.
PESTICIDES
DDT and its Metabolites. DDT, although usually considered to be very resistant
to metabolic breakdown, does metabolize nonetheless to ODD and to DDE, DDE
being the more resistant of the two (Tinsley, 1979). Levels of DDT and of
these metabolites were summed to arrive at total DDT levels. Total DDT ranges
- 37 -
-------
from zero to 2265 ug/kg with a mean total DDT level of 360 ug/kg in the Detroit
study area. As DDT is metabolized to ODD, or more completely to DDE, the con-
figuration of the parent material (p,p or o,p) is maintained. Overall, the p,p
configuration is encountered in 62% and o,p in 39% of the total DDT. (Table
14, DDT and Metabolites).
In fish total DDT is dominated by DDE (DDE>DDT>DDD)$ which is the more com-
pletely metabolized product (DeVault, 1985). Detroit sediments, however, are
dominated by ODD overall (DDT-12.2%, DDD-52.8%, DDE-34.9%), indicating less
complete metabolism, or a different metabolic pathway than in fish.
The highest total DDT value occurs at DTR82-03, near Belle Isle (2265 ug/kg),
and is predominantly ODD (69.3%). Stations DTR82-19 and DTR82-38 call atten-
tion to themselves because their distributions of DDT and metabolites are
predominantly DDT (>50%). Station DTR82-38 contains the second highest concen-
tration of total DDT in the study area. The predominance of DDT at these two
sites seems to indicate a more recent addition of DDT which has not yet been
metabolized. Thus, the greater proportion of DDT may indicate a source of the
contaminant in the study area. Alternately, conditions here may not be favor-
able for DDT metabolism.
Other Pesticides
Gamma-chlordane is the only other pervasive pesticide in the Detroit area.
Gamma-chlordane peaks are found in Conners Creek (145 ug/kg), in the Belle Isle
area (95 ug/kg), and in the Ecorse River (149 ug/kg). Relatively high levels
are evident in the northern Trenton Channel and the Rouge River (Figure 52,
Gamma Chlordane).
- 38 -
-------
Beta-BHC levels are generally low but peaks were found in Conners Creek (170
ug/kg) and above, and below the Ecorse River (195 ug/kg)(Figure 53, Beta-BHC).
Low levels of the other pesticides appear sporadically in the study area (Table
15, Pesticides).
Volatile Organics. Dichloromethane ranges from 4 ug/kg to 91 ug/kg and is pre-
sent almost everywhere in low concentrations. Highest concentrations were
found between the Rouge and Ecorse Rivers (Figure 54, Dichloromethane). Tri-
chloroethene is widely present, and ranges from 3 ug/kg to 50 ug/kg. The
highest levels are just above the entrance to the Trenton Channel (Figure 55,
Trichloroethene). Methyl benzene, ethyl benzene, 1,-3-dimethylbenzene and 1,2
and 1,4-dimethylbenzene were frequently found in the study area. Upstream on
the Rouge River, all four of these volatile organic compounds exhibit values
over an order of magnitude higher than elsewhere in the study area, indicating
the proximity of a source. (Table 16, Volatile Organics).
High background levels of dichloromethane, trichlorornethane, methyl benzene,
ethyl benzene and dimethyl benzenes may indicate upstream sources of volatiles,
perhaps on the St. Clair River. Concentrations of other volatile contaminants
in Detroit sediments are consistently lower. Of the thirteen volatile organic
contaminants found in the study area, nine are present near the mouth of the
Huron River where levels of most other groups of contaminants have been rather
low. In general, however, the various volatile organics were found mainly in
the Rouge River area and the northern Trenton Channel. Sources originating
from the steel and chemical industry, CSOs and sewage treatment plants are
implied.
- 39 -
-------
Phenols. Phenol, p-cresol and 2,4-dimethyl phenol are present in the Detroit
study area. Phenol ranges widely from 30 ug/kg to 9500 ug/kg. Relatively high
values are observed in Conners Creek in the Belle Isle area, in the Rouge River
and very high values are observed in the northern Trenton Channel. (Figure 56,
Phenol). P-cresol similarly has highs at Belle Isle, at the mouth of the Rouge
River, and in the northern Trenton Channel. Levels range from 20 ug/kg to 9910
ug/kg. (Figure 57, P-cresol).
2,4-dimethyl phenol is found primarily in the northern Trenton Channel. The
occurence of the enormously high values in this area (up to 25,100 ug/kg)
implicate coking and casting operations as a probable source of these contami-
nants to the sediments (Table 17, Phenols).
Substituted Benzenes and Substituted Cyclic Ketones
Aniline, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2-dichlorobenzene, 1,2,4-
trichlorobenzene and isophorone are present in varying quantities in the
Detroit area sediments. Their highest levels occur in Conners Creek in the
Belle Isle area, in the Rouge River and in the Trenton Channel (Table 18, Sub-
stituted Benzenes).
Hexachl orobenzene (HCB) is widely present throughout the Detroit area. Its
values range from trace levels to 106 ug/kg (Figure 58, HCB). Highest concen-
trations are found in the Trenton Channel. HCB concentrations are fairly
uniform throughout the study area implying major sources upstream from Detroit,
possibly in the Sarnia area. Local sources from the chemical industry would
explain the elevated levels in the Trenton Channel. Dibenzofuran levels range
range from zero to 3620 mg/kg. Highest levels are found in the Rouge River
area (Figure 59, Dibenzofuran).
- 40 -
-------
Phthalate Esters
Di-n-butyl phthalate and Bis(2-ethylhexyl)phthalate levels are rather high
throughout most of the study area; however, the laboratory analytical reports
indicate that impurities may have been introduced in the course of analysis.
Blanks contained up to 420 ug/kg Di-n-butyl phthalate and up to 540 ug/kg
Bis(2-ethyl hexyl phthalate). The results should therefore be used with a
degree of caution. Di-n-butyl phthalate levels range from zero to 5690 ug/kg.
Peaks are found in Conners Creek in the Belle Isle area, in downtown Detroit
(DTR82-08) and above the Ecorse River mouth.
Bis(2-ethyl hexyl) phthalate levels range from zero to 47,100 ug/kg. Peaks are
found in the Rouge River, below the mouth of the Ecorse River, and in the
northern Trenton Channel. (Figure 60, Bis(2-ethylhexyl) phthalate).
- 41 -
-------
REFERENCES
Armstrong, David E., Swackhamer, Deborah L. PCB Accumulation in Southern
Lake Michigan Sediments: Evaluation from Core Analysis in Physical
Behavior of PCBs in the Great Lakes, eds. Donald Mackay et al., Ann
Arbor, Science, 1983.
Boehm, Paul D., Farrington, John W. Aspects of the Polycyclic Aromatic
Hydrocarbon Geochemistry of Recent Sediments in the Georges Bank
Region, Environmental Science and Technology, Vol. 18., No. 11.,
1984.
Comba, M.E. and Kaiser, K.L.E. Volatile Halocarbrons in the Detroit River
River and Their Relationship with Contaminant Sources, J. Great Lakes
Res., 11(3):404, 1985.
DeVault, David. USEPA-GLNPO, Personal Communication, 2/4/85.
Eisenreich, S.J., Catel, P.O., Looney, B.P. PCB Dynamics in Lake Superior
Water In Physical Behavior of PCBs in the Great Lakes eds. Donald
Mackay et^ jil_., Ann Arbor Science, 1983.
Eldridge, J.E., Shanmugam, K., Bobalek, E.G., Simard, G.L. PAH Emissions
From Paving Asphalt in Laboratory Simulation, In Polynuclear Aromatic
Hydrocarbons: Formation Metabolism and Measurement, eds. Marcus Cooke
Anthony J. Dennis. Battelle Press, 1984
Fall on, M.E., and Horvath, R.J. Preliminary Assessment of Contaminants in
Soft Sediments of the Detroit River, J. Great Lakes Res., 11(3):
373-378, 1985.
Great Lakes Water Levels Facts, U.S. Army Corps of Engineers, Detroit Dis-
trict 1984-755-925, 1984
Griffin, R.A. and Shimp, N.F. Attenuation of Pollutants in Municipal
Landfill Leachate by Clay Minerals, EPA-600/2-78-157, August, 1978.
Griffin, R.A., Chian E.S.K. Attenuation of Water Soluble Polychlorinated
Biphenyls by Earth Materials, EPA-600/2-80-027, 1980.
Guidelines for the Pollutional Classification of Great Lakes Harbor Sedi-
ments. U.S. Environmental Protection Agency, Region V Chicago,
Illinois, April, 1977
IJC, Great Lakes Water Quality Board, 1985 Report on Great Lakes Water
Quality, June, 1985.
Milliken, J.O., Leadbetter, M.R., Carrol, R.J. Indicates of Hazard for
Polycyclic Organic Matter, in Polynuclear Aromatic Hydrocarbons:
Formation, Metabolism and Measurement, ed. Marcus Cooke and Anthony J,
Dennis, Battelle Press, Columbus, 1984.
- 42 -
-------
REFERENCES (con't)
Mozola, A.J. Geology for Land and Groundwater Planning in Wayne County,
Michigan: Report of Investigation 3, Michigan Geological Survey,
1969.
Mudroch, Alena. Geochemistry of the Detroit River Sediments, National
Water Research Institute Canada Center for Inland Wates, Burlington,
Ontario, July, 1984.
Oliver, B.G., Bourbonnierre, R.A. Chlorinated Contaminants in Surficial
Sediments of Lakes Huron, St. Clair and Erie: Implications Regarding
Sources along the St. Clair and Detroit Rivers, National Water
Research Institute, Canada Center for Inland Waters, 1984.
Palmer, Marvin. Methods Manual for Bottom Sediment Sample Collection,
USEPA Region V, May, 1985.
Swain, Lindsay. "The Potential for Great Lakes Contamination by Ground-
water in the United States." 1983 Annual Report Appendix II Ground-
water Contamination. Prepared by the Groundwater Contamination Task
Force of the Science Advisory Board of the International Joint Com-
mission, February, 1985, Windsor, Ontario.
Thornley, S., Hamdy, Y. An Assessment of the Bottom Fauna and Sediments
of the Detroit River, Ontario Ministry of the Environment, February,
1984.
Tinsley, Ian J. Chemical C oncepts in Pollutant Behavior, John Wiley and
Sons, New York, 1979.
Toxic Chemical Issues and Research Priorities 1985-1986, Great Lakes Water
Quality Program. In the Department Committee on Water/Great Lakes
Working Group/Toxic Chemicals Committee, September, 1984.
Water Resources Data for Michigan, Water Year 1983 USGS WRD, Lansing,
Michigan, 1983.
Wisler, C.O., Stramel, G.J., Laird, L.B. Water Resources of the Detroit
Area Michigan, U.S. Geological Survey, Circular 183, 1952.
Work Quality Assurance Plan. 1982 Detroit, Michigan Area Sediment Survey
Work/Quality Assurance Plan, USEPA Great Lakes National Program
Office Chicago, Illinois, 1985.
- 43 -
-------
Appendix A
Guidelines for the Pollutional Classification
of Great Lakes Harbor Sediments
U.S. Environmental Protection Agency
Region V
Chicago, Illinois
April , 1977
-------
Guidelines for the evaluation of Great Lakes 'harbor sediments, based on bulk
sediment analysis, have been developed by Region V of the U.S. Environmental
Protection Agency. These guidelines, developed under the pressure of the need
to make immediate decisions regarding the dispoal of dredged material, have not
been adequately related to the impact of the sediments on the lakes and are
considered interim guidelines until more scientifically sound guidelines are
devel oped.
The guidelines are based on the following facts and assumptions:
1. Sediments that have been severely altered by the activities of
man are most likely to have adverse environmental impacts.
2. The variability of the sampling and analytical techniques is
such that the assessment of any sample must be based on all
factors and not on any single parameter with the exception of
mercury and polychl orinated biphenyls (PCRs).
3. Hue to the documented bioaccumulation of mercury and PCBs, rigid
limitations are used which override all other considerations.
Sediments are classified as heavily polluted, moderately polluted, or nonpol-
luted by evaluating each parameter measured against the scales shown below.
The overall classification of the sample is based on the most predominant
classification of the individual parameters. Additional factors such as elu-
triate test results, source of contamination, particle size distribution,
benthic macroinvertebrate populations, color, and odor are also considered.
These factors are interrelated in a complex manner and their interpretation is
necessarily somewhat subjective.
A2
-------
The following ranges, used to classify sediments from Great Lakes harbors are
based on compilations of data from over 100 different harbors since 1967.
NONPOLLUTEn MODERATELY POLLUTED HEAVILY POLLUTED
Volatile Solids (%) <5 5-8 >8
COP (ng/kg dry weight) <40,000 40,000-80,000 >80,000
TKN (mg/kg dry weight) < 1,000 1,000- 2,000 > 2,000
Oil and Grease < 1,000 1,000- 2,000 > 2,000
(Hexane Solubles)
(mg/kg dry weight)
Lead (mg/kg dry weight) <40 40-60 >60
Zinc (mg/kg dry weight) <90 90-200 >200
The following supplementary ranges used to classify sediments from Great Lakes
harbors have been developed to the point where they are usable but are still
subject to modification by the addition of new data. These ranges are based on
260 samples from 34 harbors sampled during 1974 and 1975.
NONPOLLUTED MODERATELY POLLUTED HEAVILY POLLUTED
Ammonia (mg/kg dry weight)
Cyanide
Phosphorus " "
Iron " "
Nickel
Manganese " "
Arsenic
Cadmi urn " "
Chromium
Barium " "
Copper " "
<75
<0.10
<420
<17,000
<20
<300
<3
*
<25
<20
<25
75-200
0.10-0.25
420-650
17,000-25,000
20-50
300-500
3-8
*
25-75
20-60
25-50
>200
>0.25
>650
>25,000
>50
>500
>8
>6
>75
>60
>50
*Lower limits not established
A-3
-------
The guidelines stated below for mercury and PCB's are based upon the best
available information and are subject to revision as new information becomes
avail able.
Methylation of mercury at levels >_ 1 mg/kg has been documented (1,2). Methyl
mercury is directly available for bioaccumulation in the food chain.
Elevated PCB levels in large fish have been found in all of the Great Lakes.
The accumulation pathways are not well understood. However, bioaccumulation
of PCPs at levels >_ 10 mg/kg in fathead minnows has been documented (3).
Because of the know bioaccumulation of these toxic compounds, a rigid limita-
tion is used. If the guidelines values are exceeded, the sediments are classi-
fied as polluted and unacceptable for open lake disposal, no matter what the
other data indicate.
POLLUTED
Mercury _> 1 mg/kg dry weight
Total PCBs _>_ 10 mg/kg dry weight
The pollutional classification of sediments with total PCB concentrations bet-
between 1.0 mg/kg and 10.0 mg/kg dry weight will be determined on a case-by-
case basis.
a. Flutriate Test Results
The elutriate test was designed to simulate the dredging and dispoal pro-
cess. In the test, sediment and dredging site water are mixed in the ratio
of 1:4 by volume. The mixture is shaken for 30 minutes, allowed to settle
for 1 hour, centrifuged, and filtered through a 0.45 u filter. The fil-
tered water (elutriate water) is then chemically analyzed.
A-4
-------
A sample of the dredging site water used in the elutriate test is filtered
through a 0.45 u filter and chemically analyzed.
A comparison of the elutriate water with the filtered dredging site water for
for like constituents indicates whether a constitutent was or was not released
in the test.
The value of elutriate test results are limited for overall pollutional class-
ification because they reflect only immediate release to the water column under
aerobic and near neutral pH conditions. However, elutriate test results can be
used to confirm releases of toxic materials and to influence decisions where
bulk sediment results are marginal between two classifications. If there is
release or non-release, particularly of a more toxic constituent, the elutriate
test results can shift the classification toward the more polluted or the less
polluted range, respectively.
b. Source of Sediment Contamination
In many cases the sources of sediment contamination are readily apparent. Sed-
iments reflect the inputs of paper mills, steel mills, sewage discharges, and
heavy industry very faithfully. Many sediments may have moderate or high con-
centrations of TKN, COD, and volatile solids yet exhibit no evidence of man
made pollution. This usually occurs when drainage from a swampy area reaches
the channel or harbor, or when the project itself is located in a low lying
wetland area. Pollution in these projects may be considered natural and some
leeway nay be given in the range values for TKN, CODS and volatile solids pro-
vided that toxic materials are not also present.
A-5
-------
c. Field Observations
Experience has shown that field observations are a most reliable indicator of
sediment condition. Important factors are color, texture, odor, presence of
detritus, and presence of oily material.
Color. A general guideline is the lighter the color the cleaner the sediment.
There are exceptions to this rule when natural deposits have a darker color.
These conditions are usually apparent to the sediment sampler during the sur-
vey.
Texture. A general rule is the finer the material the more polluted it is.
Sands and gravels usually have low concentrations of pollutants, while silts
usually have higher concentrations. Silts are frequently carried from polluted
upstream areas, whereas, sand usually comes from lateral drift along the shore
of the lake. Once again, this general rule can have exceptions and it must be
applied with care.
Odor. This is the odor noted by the sampler when the sample is collected.
These odors can vary widely with temperature and observer and must be used
carefully. Lack of odor, a beach odor, or a fishy odor tends to denote cleaner
samples.
netritus. Detritus may cause higher values for the organic parameter COD, TKN,
and volatile solids. It usually denotes pollution from natural sources. Note:
The detemination of the "naturalness" of a sediment depends upon the estab-
lishment of a natural organic source and a lack of man made pollution sources
with low values for metals and oil and grease. The presence of detritus is not
decisive in itself.
A-6
-------
REFERENCES
Halter, M.T., and Johnson, H.E., "A Model System to Study the Release of
PCB from Hydrosoils and Subsequent Accumulation by Fish," presented
to American Society for Testing and Materials, Symposium on Aquatic
Toxicology and Hazard Evaluation," October 25-26, 1976, Memphis,
Tennesse.
Jensen, S., and Jernelov, A., "Biological Methylation of Mercury in Aquatic
Organisms," Nature, 223, August 16, 1969 pp 753-754.
Magnuson, J.J., Forbes, A., and Hall, R., "Final Report - An Assessment of
the Environmental Effects of Dredged Material Dispoal in Lake
Superior - Volume 3: Biological Studies," Marine Studies Center,
University of Wisconsin, Madison, March, 1976.
-------
APPENDIX B
Analytical Method Documentation
Parameters
Units
Title/Description
Non-volatil e
organics:
acidic &
base
neutral s,
other
organics
hy GC/MS
mg/kg
dry
weight
Volatile
organic
by/purge
& trap
RC/MS
ug/kg
dry
weight
basis
PCBs
Pesti-
cides
GC/EC
mg/kg
dry
weight
basis
"Standard Operating Procedure for the analysis of
sediments for Non-volatile Organic Compounds:
Embayment and Nearshore Program CRL Method No.:
"TOX105631" Based on USEPA Method 625 [Federal
Register 1979].
Sediments are air dried, sieved and soxhlet extracted
with 1:1 acetone/hexane for 16 hours. Extracts are
screened by fiC/FID and diluted or concentrated as
needed. GC/MS protocol found in "Standard Operation
Procedure GC/MS/DS Analysis of Non-Volatile Organic
Compounds CRL Method No.: TOX9561, TOX9571, TOX95631,
TOX95731".
Compounds are quantitated against standards when
available or an estimated concentration is reported
on the basis of the response of the internal standard,
n-10 phenanthrene.
"Analysis of Volatile Organic Compounds in Fish,
Sediment, and Water Samples Using GC/MS, CRL Method No.
TOX10B631, 105731, 10561, 10571" Based on USEPA Method
624 [Federal Register 1979].
Wet samples are purged with helium for 4 minutes and
the organics are trapped on a Tenax trap. The trap
is desorbed onto the GC column for analysis. Compounds
are quantified using standards when available, or are
estimated against the response of the internal standard
2-bromo-l-chloropropane.
"Analysis of Pesticides, Phthalates, and Polychlorinated
Biphenyls in Soils and Bottom Sediments, CRL Method No.
PES1262-84, 17119-17125" Based on USEPA Method 608
[Federal Register 1979].
Samples are air dried, sieved and soxhl et extracted
with 1:1 acetone/hexane for 16 hours. Extracts are
cleaned up by Florisil column chromatography. Further
separation of PCBs from Pesticides is done with
silica gel column chromatography. The extracts are
screened by GC/EC. Samples are quantified and
confirmed by GC/EC. GC/MS analysis of the ABN extracts
is used for additional confirmation.
B-l
-------
APPENDIX B (con't)
Parameters
Units
Title Description
Ag, Al , B, Ba,
Be, Cd, Co, Cr
Cu, Fe, Li, Mn
Mo, Ni, Pb, Sn
Sr, V, Y, Zn,
Ca, K, Mg, Na
CN
Phenol
Ammonia as N
Sediment Sample
preparation
Total Phosphorus
Total Phosphorus
Kjeldahl Nitrogen
as N
Chemical Oxygen
Demand
Mercury
Arsenic
Sel eni urn
Volatile Solids
% Solids
Oil & Grease
mg/kg
dry
weight
basis
mg/kg dry
weight basis
mg/kg dry
weight basis
mg/kg dry
weight basis
mg/kg dry
weight basis
mg/ kg d ry
weight basis
mg/ kg dry
weight basis
mg/ kg dry
weight basis
% of
total solids
% dry weight (g)
wet weight (g)
mg/kg dry
weight
"Preparation of Sediments and Other Solids for
ICAP Analysis" Central Regional Laboratory
(CRL) Method #MET 413. "Standard Operative
Procedure (SOP) for the Determination of Total
Metals in Water by ICAP CRL Method #MET 111"
Reference IJSEPA 1979a.
"SOP for Total Cyanide, CRL Method #MIN 71919"
Reference IJSEPA 1979b.
"SOP: Phenols, Total Recoverable, CRL Method
#MIN74818" Reference USEPA 979b.
CRL SOP for preparation of sediment and solids fo
Ammonia - N, TKN, TP and COD
"SOP: Ammonia Nitrogen, CRL Method #MIN 7294"
Reference USEPA 1979b. "SOP for Total Phos-
phorus and Total Kjeldaahl Nitrogen, CRL Method
#MIN 7315, MIN 7304," Reference USEPA 1979b.
"SOP: COD, CRL Method #MIN 7336" Reference USEPA
1979b.
"SOP: Total Mercury in Fish and Sediments, CRL
Method #Min 7336" Reference USEPA 1979b.
"SOP for the Determination of Arsenic and Sel eniui
in sediments and Other Solids by Furnace AA, CRL
Method #MET 463, Met 4213" Reference USEPA 1979b
"SOP for Total Volatile Solids (%) in Sediments
and Solids, CRL Method #447" Gravimetric deter-
mination at 550°C + 50°C.
"SOP for Total Residue (% Solids), CRL Method
#444" Gravimetric determination.
PES 10423643
B-2
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APPENDIX R (con't)
Data Quality Requirements and Assessments
Parameter
Total solids
Volatil e solids
COD
Total Kj el da hi N
Total P
Hg
Ammonia N
Cyanide
ICAP metal s
Acid , Rase,
Neutral
Priority
Pollutants
Pesticides
PCRs
Volatile
Priority
Pol lutants
Oil & Grease
Arsenic
* See Table 1
Sam pi e
Matrix
Sediment
Detection
Limit
1%
1%
100 mg/kg
0.05 mg/kg
0.02 mg/kg
0.1 mg/kg
0.1 mg/kg
0.1 mg/kg
*
*
*
*
650 mg/ kg
2 mg/kg
Estimated
Accuracy
10%
10%
20%
20%
20%
20%
20%
20%
5%
50%
50%
50%
i 10%
Accuracy
Protocol
1 Spike
For
Every
10
Sam pi e
Estimated
Precision
10%
10%
20%
20%
20%
20%
20%
20%
20%
50%
50%
50%
To be
estab-
1 i shed
2 ug/kg
Precision
Protocol
One
Duplicate
For
Every
10
Sampl es
B-3
-------
Table 1. Organic Compounds Sought in Sediments by the GC/MS Method and
Maximum Detection Limits
(Actual detection limits for individual samples may vary as a function of
interferences present, aliquot size, degree of pre-concentration, etc.
Actual detection limits for some subsets of the overall data base were up
to an order to magnitude less than the maximum detection limits listed
here.)
BASE AND NEUTRAL NON-VOLATILE ORGANICS (GC/MS)
MAXIMUM
DETECTION
NAME LIMIT (ug/kg)
Aniline 50
Bis(2-Chloropthyl) ether 50
1,3-Dichlorobenzene 60
1,4-Dichl orobenzene 60
1,2-Dichlorobenzene 60
Benzyl Alcohol 150
Bis(2-Chloroisopropyl)ether 160
Hexachl oroethane 140
N-nitrosodipropyl amine 90
Nitrobenzene 70
Isophorone 30
Bi s(2-Chl oroethoxy)methane 50
1,2,4-Trichlorobenzene 70
Naphthalene 20
4-Chloroaniline 60
Hexachlorobutadiene 120
2-Methylnapthalene 30
Hexachl orocyclopentadiene 230
2-Chloronaphthalene 40
Acenaphthylene 30
Dimethyl phthal ate 30
2,fi-ninitrotoluene 160
Acenaphthene 40
3-Nitroanil ine 250
Dibenzofuran 40
2,4-Dinitrotoluene 170
Fluorene 50
4-Chl orophenyl phenyl ether 90
Diethyl phthal ate 40
4-Ni troanil ine 570
Diphenylamine (N-Nitroso-) 80
l,?-Di phenylhydrazine 50
4-Bromophenylphenyl ether 160
Hexachl orobenzene 130
Phenanthrene 70
Anthracene 70
Di-N-butyl phthal ate 260
Cl
-------
TARLF 1 (con't)
RASE AND NEHTRALNON-VOLATILE ORGAN1CS (GC/MS
MAXIMUM
DETECTION
NAME LIMIT (ug/kg)
Fluoranthene 150
Pyrene 170
Benzyl butyl phthal ate 420
Benzo(a)anthracene & Chrysene 830
B1s(2-ethylhexyl)phthal ate 270
ni-N-octylphthlate 370
Benzo(R«/K)fluoranthene 1260
Benzo(A)pyrene 1500
Indeno[l,2,3-Cnlpyrene 1570
Dibenzo(A,H)anthracene 2030
Benzo(GHI)perylene 1570
ACIDIC NON-VOLATILE ORRANICS (GC/MS)
Phenol 50
2-Hhl orophenol 60
2-Methyl phenol 70
4-Methylphenol 50
?-Nitrophenol 120
2,4-nimethylphenol 70
2,4-Dichlorophenol 70
Renzoic Acid 160
4-Chl oro-3-methylphenol 90
(2,4,5 & 2,4,6)-Trichl orophenol 150
2,4-Dinitrophenol 1360
4-Nitrophenol 680
2-Methyl-4,6-Dinitrophenol 770
Pentachlorophenol 720
C2
-------
TABLE 1 (con't)
VOLATILE ORGANICS (RC/MS)
Name
Dichloromethane
1,1-nichloroethene
1,1-Dichloroethane
1,2-Dichloroethene
Trichloromethane
1,2-Dichl oroethane
1,1,1-Trichloroethane
Tetrachloromethane
Bromodichloromethane
1,2-Dichl oropropane
1,3-Dichloro-l-propene (Trans)
Trichloroethene
Benzene
Dibromochl oronethane
1,1,2-Trichloroethane
1,3-Dichloro-l-Propene (Cis)
Tribromomethane
1,1,2,?,-Tetrachl oroethane
Tetrachloroethene
Methyl benzene
Chlorobenzene
Ethyl benzene
1,3-Dinethyl benzene
!,?-&!,4-nimethylbenzene
Maximum
Detection
Limit (ug/kg)
0.3
0.2
0.1
0.2
0.1
0.3
0.2
0.2
0.2
0.2
0.1
0.2
0.1
0.2
0.3
0.3
0.5
0.2
0.2
0.1
0.1
0.1
0.1
0.1
C3
-------
TABLE 1 (con't)
PESTICIDES
Maximum
Detection
Name Limit (ug/kg)
Triflan(Trifluralin) 180
Alpha-BHC 330
Hexachlorobenzene 150
2,4-D, Isopropyl ester 400
Gamma-BHC 3140
Reta-BHC 540
Heptachlor 450
Pi-butylphthal ate 240
Zytron 280
Aldrin 470
DCPA 220
Isodrin 410
Heptachlor epoxide 660
Oxychlordane 2860
Gamma chlordane 490
o,p ODE 250
Endosulfan-I 1900
p,p DDE 380
Dieldrin 150
o,p nnn 230
Endrin 1120
Chi orobenzi late 300
Endosulfan-II 2620
O,P-DDT & p,p-nnn 530
Kepone(chlordecone) 950
p,p DDT 400
Methoxychlor 330
Tetradi fon 2730
Mi rex 480
C4
-------
TABLE 1 (con't)
PCBs (GC/MS)
Name
Monochlorobiphenyls (total)
Di chl orobi phenyl s (total)
Trichl orobiphenyls (total)
Tetrachl orobi phenyl s (total)
Pentachlorobiphenyl s (total)
Hexachl orobiphenyl s (total)
Heptachl orobiphenyls (total)
Maximum
Detection
Limit (ug/kg)
410
290
390
520
520
330
580
C5
-------
Table 2. Pesticides and PCRs Sought in Sediments by the GC/EC Method
Aroclor 124?
Aroclor 1248
Aroclor 1254
Aroclor 1260
o.p-DDE
p.p-DFE
o,p-nnn
p,p-nnn
o,p-nni
p.p-DDT
G-Chlordane
Oxychl ordane
Heptachlor epoxide
Zytron
B-RHC
G-BHC
Hexachlorobenzene
Trifluralin
Aldrin
Mi rex
Heptachlor
Methoxychlor
Endrin
DC PA
Endosulfan-I
Endosulfan-II
Dieldrin
C6
-------
Table 3. Metals Analyzed and Their Detection Limits
Metal
Silver
Al umi num
Boron
Barium
Beryllium
Cadmium
Cobalt
Chromium
Copper
Iron
Lithium
Manganese
Molybdenum
Nickel
Lead
Tin
Strontium
Vanadium
Yttrium
Zinc
Calcium
Potassium
Magnesium
Sodium
Mercury
jletection Limit (mg/kg)
0.3
8
8
0.5
0.1
0.2
0.6
0.8
0.6
8
1
0.5
1
1.5
7
4
1
0.5
0.5
4
50
100
10
100
0.2
C7
-------
STATION # LATITUDE
TABLE 4
LONGITUDE
DTR82-01
DTR82-03
DTR82-05A
DTR82-08
DTR82-13
DTR82-19
ROR82-07
ROR82-06
ROR82-02
DTR82-22
DTR82-23
DTR82-25
DTR82-26
DTR82-27
DTR82-52
DTR82-53
DTR82-29
DTRS2-30
DTR82-3?
DTR82-38
DTR82-56
PTR82-49
DTR82-43A
DTR82-45
DTR82-48
HUR82-02
HUR82-01
DTR82-57
42 21 24
42 21 22
42 21 20
42 20 04
42 18 48
42 16 41
42 17 23
42 17 45
42 16 53
42 15 39
42 15 35
42 15 21
42 14 37
42 14 31
42 14 38
42 14 00
42 14 06
42 13 38
42 12 36
42 10 25
42 03 02
42 08 53
42 07 15
42 06 51
42 03 42
42 03 39
42 02 31
42 03 02
82 56 10
82 57 13
82 58 22
83 01 08
83 04 41
83 06 30
83 10 04
83 09 12
83 07 07
83 07 02
83 07 06
83 07 16
83 08 01
83 08 13
83 09 35
83 09 45
83 08 51
83 08 49
83 08 39
83 09 53
83 12 48
83 10 25
83 10 55
83 10 53
83 11 23
83 14 48
83 12 50
83 12 48
DETROIT 1982 FIELD OBSERVATIONS
DEPTH
DATE TIME (FEET) COLOR
DESCRIPTION
ODOR
OIL
82/10/28
82/10/28
82/10/28
82/10/28
82/10/27
82/10/27
82/10/28
82/10/28
82/10/28
82/10/27
82/10/27
82/10/27
82/10/27
82/10/27
82/10/28
82/10/28
82/10/27
82/10/27
82/10/27
82/10/27
82/10/27
82/10/27
82/10/26
82/10/26
82/10/26
82/10/28
82/10/28
82/10/28
11 15
11 00
10 30
09 45
17 30
16 40
13 40
13 50
12 35
16 45
16 30
16 10
15 14
15 05
15 55
16 10
14 56
14 45
14 20
12 35
12 05
11 59
17 04
15 52
15 00
17 49
17 29
17 20
05
17
11
09
10
16
05
17
21
14
21
05
23
08
0
0
04
03
04
01
02
02
29
04
03
02
01
02
DK GRA/BLK
GRA/BRN
BRN/BLK
GRA/BRN
BLK
BLK
-
BRN
BLK/BRN
GRA/BLK
GRA
GRA
GRA
BLK/GRA
BLK
GRA/BRN/BLK
BRN
GRA
GRA/BLK
BLK/DK GRA
BLK
BLK
BLK
BRN/GRA
GRA/BRN
GRA/BRN
OK GRA
BLK=BLACK
GRA=GRAY
BRN=BROWN
DK=DARK
ST/CL
ST/CL
SD/ST
CL
MK/CO
BUB.MK
-
SD/MK
MK
MK
ST/SD
CL
ST/CL
SD/ST
MK
SD/CL
CL/SD/GRV
CL/SD
MK
CL/SD/MK
CL/ORG OZ
ST/CL
ST/SD
SD/ST/CL
SD
CL/SD/GRV
ORG OZ/CL
CL=CLAY
SD=SAND
ST=SILT
MK=MUCK
CO=COAL
BUB=BUBLING
ORG=ORGANIC
OZ*OOZE
GRV=GRAVEL
0
E
0
C
0
-
-
-
0
E/0
E
E
0
0
0/C
E
E
N
0
E
S
E
E
E
E
E
E
E= EAR THY
0=OILY
C=CHEMICAL
S=SEPTIC
N=NONE
Y
N
Y
N
Y
-
-
N
Y
Y
N
N
N
Y
-
N
N
N
Y
N
N
Y
N
N
N
-
N
Y=YES
N=NO
00
o
-------
TABLE 5 CONVENTIONAL POLLIfTANTS IN DETROIT 19R2 SEDIMENTS
(1977 USEPA SEDIMENT GUIDELINES)
TOTAL
TOTAL VOLATILE
TAT I ON f
TR82-01
1 r\ \tc. * ' A
TR82-03
TR82-05A
TR82-08
TR82-13
TR82-19
OR82-07
OR82-06
OR82-02
TR82-22
(TR82-23
TR82-25
)TR82-26
ITR82-27
1TR82-52
ITR82-53
JTR82-29
)TR82-30
1TRS2-32
)TR82-38
VTR82-56
1TR82-49
1TR82-43A
)TR82-45
1TR82-48
-UJR82-02
HHR82-01
VTR82-57
LEGEND:
HIGHEST
T=Value
W=Value
under
SOL I PS
SOLIDS
(PERCENT) ^PERCENT)
65.7
37.7
43.5
28.7
58.4
40.7
25.2
39.9
50.4
51.3
43.9
37.6
49.8
51.4
49.4
33.3
46.5
52.2
49.9
36.9
49.9
49.0
58.1
45.5
48.4
62.6
50.5
48.8
HEAVILY POLLIFTEn
MODERATELY POLLUTED
NON-POLLUTED
LEVEL IN STUDY AREA
reported is less than
reported is less than
"r code.
5.6+
11.6*
4.2
10.0*
5.6+
18.4*
23.4**
10.4*
8.1*
9.5*
10.2*
10.1*
3.6
11.2*
10.4*
10.3*
10.0*
7.4+
10.0*
12.2*
12.7*
10.6*
8.1*
10.0*
9.6*
?.d
6.4+
4.9
= *"
= +
=
= **
OIL
A
GREASE
(ng/kg)
36390*
5215*
31100*
5769*
22350*
15060*
35550*
5407*
12040*
23400*
15250*
13940*
38990**
8345*
14830*
3087*
1752+
1795+
cr teria of detect
lowest
CHEMICAL
OXYGEN
DEMAND
(mg/kg)
46000+
180000*
65000+
160000*
67000+
150000*
300000**
190000*
130000*
170000*
180000*
170000*
33000
200000*
180000*
130000*
150000*
150000*
170000*
230000*
220000*
170000*
110000*
150000*
140000*
31000
54000+
56000+
ion
TOTAL
KJELDAHL
NITROGEN
(mg/kg)
870.0
3300.0*
1000.0+
2800.00*
1200.0+
2400.0*
8600.0**
2600.0*
2800.0*
1900.0+
3100.0*
3700.0*
720.0
3400.0*
3100.0*
3300.0*
2800.0*
1900.0+
1900.0+
3200.0*
3300.0*
2000.0+
1400.0+
1500.0+
2500.0*
640.0
1300.0+
2000.0+
AMMONIA
-M
(mg/kg)
50.0
530.0*
70.0
470.0+
110.0+
190.0+
1400.0**
470.0*
60.0
300.0*
640.0*
970.0*
50.0
1000.0*
100.0+
340.0*
510.0*
310.0*
370.0*
510.0*
650.0*
260.0*
210.0*
230.0*
180.0+
60.0
100.0+
90.0+
PHOSPHORUS
-P
(mg/kg)
350.0
2100.0*
480.0+
2100.0*
540.0+
910.0*
3300.0*
2000.0*
1200.0*
2900.0*
2200.0*
2300.0*
670.0*
6400.0*
1300.0*
1400.0*
2700.0*
2600.0*
3300.0*
4700.0*
6200.0*
4800.0*
6700.0**
6200.0*
3700.0*
370.0
790.0*
720.0*
CYANIDE
(mg/kg)
0.10W+
12.00 *
0.10W+
7.90 *
7.10 *
15.00 *
33.00 **
5.80 *
3. DOT*
3.00T*
4. DOT*
3.00T*
0.10W+
19.00 *
2.00T*
0.10W+
4.00T*
4.00T*
5.10 *
12.00 *
14.00 *
3.00T*
LOOT*
5.00 *
0.10W+
0.10W+
0.10W+
0.10W+
value reported
en
-------
TABLE f) METALS IN DE FRUI ! iy»Z bklHMhNIb
(1977 USEPA GUIDELINES)
LEAD ZINC IRON NICKEL MANGANESE CADMIUM CHROMIUM BARIUM COPPER MERCURY
j I r\ i i * " - rr
DTR82-01
TTR82-03
3TR82-05A
1TR82-08
1TR82-13
TTR82-19
WR82-07
}OR82-06
?OR82-02
1TR82-22
1TR82-23
1TR82-25
1TR82-26
TTR82-27
TTR82-52
TTR82-53
VTR82-29
VTR82-30
DTR82-32
TTR82-38
DTR82-56
TTR82-49
1TR82-43A
VTR82-45
1TR82-48
HUR82-02
HUR82-01
3TRR2-57
LEGEND:
HIGHEST
T= Value
67.0* 90.0+
81D.O** 1300.0*
86.0* 170.0*
600.0* 1100.0*
210.0* 230.0*
670.0* 2900.0*
590.0* 1100.0*
500. n* 1100.0*
230.0* 470.0*
340.0* 1300.0*
360.0* 1100.0*
220.0* 580.0*
46.0+ 160.0+
510.0* 1300.0*
620.0* 750.0*
380.0* 470.0*
330.0* 650.0*
280.0* 750.0*
340.0* 930.0*
570.0* 3500.0**
490.0* 1500.0*
400.0* 1000.0*
210.0* 710.0*
280.0* 970.0*
99.0* 420.0*
42.0+ 140.0+
21.0 76.0
73. 0* 190.0+
HEAVILY POLLUTED = *
MODERATELY POLLUTED = +
NON-POLLUTED =
LEVEL IN STUDY AREA =**
reported Is less than en
10000.0
26000.0*
13000.0
25000.0+
19000.0+
66000.0*
42000.0*
40000.0*
20000.0+
89000.0**
71000.0*
42000.0*
30000.0*
44000.0*
25000.0+
28000.0*
40000.0*
49000.0*
43000.0*
39000.0*
63000.0*
50000.0*
59000.0*
61000.0*
25000.0+
11000.0
29000.0*
16000.0
16.0
130.0*
27.0+
83.0*
26.0+
84.0*
200.0*
65.0*
84.0*
220.0*
130.0*
96.0*
34.0+
290.0*
35.0+
42.0+
89.0*
150.0*
150.0*
190.0*
160.0
930.0*
220.0
450.0+
450.0+
1500.0*
720.0*
790.0*
410.0+
1100.0*
830.0*
630.0*
580.0*
760.0*
820.0*
580.0*
560.0*
540.0*
630.0*
750.0*
300.0** 1100.0*
180.0*
97.0*
110.0*
67.0*
15.0
22.0+
28.0+
teria of
detection
880.0*
810.0*
850.0*
430.0+
410.0+
2800.0**
290.0
0.3
24.0*
2.0
11.0*
0.6
7.9*
96.0**
10.0*
4.2*
6.9*
6.9*
4.9
0.4
16.0*
4.4
2.2
4.9
8.4*
13.0*
19.0*
25.0*
15.0*
8.1*
13.0*
5.4
0.6
0.2T
1.0
18.0
210.0*
30.0+
150.0*
65.0+
86.0*
630.0*
270.0*
95.0*
230.0*
180.0*
130.0*
32.0+
560.0*
99.0*
56.0+
170.0*
280.0*
320.0*
440.0*
680.0**
420.0*
160.0*
240.0*
92.0*
9.8
15.0
22.0
36.0+
500.0**
64.0*
260.0*
120.0*
120.0*
370.0*
210.0*
130.0*
170.0*
140.0*
130.0*
99.0*
410.0*
170.0*
190.0*
180.0*
230.0*
240.0*
300.0*
370.0*
260.0*
160.0*
250.0*
110.0*
48.0+
110.0*
70.0*
28.0+
160.0*
42.0+
160.0*
99.0*
110.0*
720.0**
280.0*
130.0*
200.0*
180.0*
140.0*
46.0+
270.0*
99.0*
110.0*
130.0*
180.0*
220.0*
220.0*
290.0*
190.0*
120.0*
190.0*
75.0*
17.0
22.0
28.0+
0.3
1.2*
0.4
1.4*
0.3
0.8
2.4*
1.1*
0.7
0.6
0.8
0.3
1.0*
0.4
0.7
1.2*
1.1*
1.3*
3.6**
1.8*
3.0*
1.6*
3.4*
1.2*
0.2T
0.3
0.2T
-------
TABLE 7 TRACE METALS IN DETROIT 1982 SEDIMENTS (mg/kg)
STATION #
DTR82-01
DTR82-03
DTR82-05A
DTR82-08
DTR82-13
DTR82-19
ROR82-07
ROR82-06
ROR82-02
DTR82-22
OTR82-23
DTR82-25
DTR82-26
DTR82-27
DTR82-52
DTR82-53
DTR82-29
DTR82-30
DTR82-32
DTR82-38
DTR82-56
DTR82-49
DTR82-43A
DTR82-45
DTR82-48
HUR82-02
HUR82-01
DTR82-57
MOLYB
SILVER BORON BERYLIUM COBALT LITHIUM DENUM TI_N STRONTIUM VANADIUM
0.3T
2.5
0.3T
1.5
0.3T
0.3T
4.9
2.3
1.8
0.3T
0.3T
0.3T
0.3T
5.9**
0.3T
0.8
i.n
1.7
3.0
3.9
5.4
2.7
0.3T
0.3T
0.3T
0.3T
0.3T
0.3T
8.0T
18.0
9.5
27.0**
9.2
9.8
14.0
13.0
11.0
25.0
8.8
11.0
12.0
15.0
13.0
8.6
11.0
12.0
13.0
14.0
14.0
13.0
14.0
11.0
8.0T
8.0T
8.3
12.0
0.2
O.IT
O.IT
0.1
8.9
O.IT
0.9
0.8
0.5
9.8**
O.IT
O.IT
O.IT
0.3
1.0
0.8
O.IT
O.IT
0.4
0.3
O.IT
0.1
O.IT
0.4
0.3
0.2
0.5
0.5
5.0
13.0
8.2
12.0
17.0**
9.9
12.0
10.0
10.0
16.0
13.0
12.0
11.0
14.0
9.5
12.0
11.0
11.0
11.0
12.0
13.0
11.0
9.0
11.0
7.9
4.7
9.2
7.5
13.0
27.0
16.0
22.0
21.0
16.0
26.0
24.0
22.0
20.0
22.0
25.0
28.0**
27.0
24.0
25.0
21.0
23.0
22.0
28.0**
25.0
25.0
16.0
21.0
16.0
14.0
21.0
19.0
LOT
7.7
LOT
3.9
7.3
2.1
10.0
16.0**
3.2
14.0
8.7
3.4
1.9
8.7
2.6
4.2
7.0
5.8
7.0
5.7
9.7
6.7
7.5
6.1
2.2
1.6
3.3
1.8
5.4
62.0**
5.3
27.0
31.0
46.0
29.0
37.0
12.0
14.0
23.0
15.0
6.0
41.0
14.0
16.0
19.0
16.0
29.0
45.0
55.0
32.0
13.0
21.0
8.0
4.0T
4.0T
8.1
25.0
93.0
34.0
75.0
84.0
79.0
110.0
80.0
47.0
59.0
50.0
54.0
160.0
78.0
120.0
110.0
76.0
81.0
160.0
220.0
120.0
110.0
100.0
230.0**
57.0
90.0
94.0
190.0
14.0
28.0
17.0
26.0
34.0
22.0
40.0**
31.0
23.0
22.0
23.0
25.0
22.0
28.0
36.0
33.0
26.0
26.0
23.0
32.0
30.0
27.0
22.0
23.0
17.0
12.0
22.0
20.0
YTTRIUM
5.6
10.0
7.5
8.9
8.9
7.4
10.0
10.0
8.5
7.7
8.7
9.3
10.0
9.3
12.0**
11.0
9.1
9.0
9.1
9.9
8.9
8.9
7.5
8.0
9.0
6.9
9.8
8.8
** Highest value in study area.
T=Value reported is less than criteria of detection.
-------
TABLE 8 MAJOR METALS IN DETROIT 1982 SEDIMENTS (tng/kg)
STATION I CALCIUM POTASSIUM MAGNESIUM SODIUM ALUMINUM
DTR82-01
DTR82-03
DTR82-05A
DTR82-08
DTR82-13
DTR82-19
ROR82-07
ROR82-06
ROR8P-02
DTR82-22
DTR82-23
DTR82-25
DTR82-26
DTR82-27
DTR82-52
DTR82-53
DTR82-29
DTR82-30
DTR82-32
DTR82-38
DTR82-56
DTR82-49
DTR82-43A
DTR82-45
DTR82-48
HUR82-02
HUR82-01
DTR82-57
T=Value reported is less than criterion of detection.
28000.0
62000.0
31000.0
58000.0
46000.0
46000.0
44000.0
43000.0
43000.0
43000.0
41000.0
41000.0
92000.0
50000.0
47000.0
42000.0
41000.0
44000.0
92000.0
87000.0
54000.0
59000.0
54000.0
81000.0
31000.0
86000.0
66000.0
44000.0
600.0
1500.0
0.0
1200.0
900.0
1000.0
2000.0
1500.0
1100.0
1100.0
1000.0
1100.0
1800.0
1800.0
1500.0
1400.0
1300.0
1500.0
1300.0
1600.0
1400.0
1500.0
1000.0
1000.0
900.0
700.0
700.0
1300.0
14000.0
17000.0
17000.0
14000.0
17000.0
13000.0
14000.0
14000.0
20000.0
17000.0
19000.0
17000.0
18000.0
17000.0
15000.0
14000.0
15000.0
15000.0
16000.0
17000.0
18000.0
22000.0
16000.0
19000.0
10000.0
14000.0
17000.0
9400.0
100. OT
300.0
100.0
200.0
200.0
300.0
700.0
200.0
200.0
200.0
200.0
200.0
200.0
300.0
500.0
600.0
200.0
200.0
400.0
500.0
300.0
300.0
1600.0
500.0
200.0
200.0
200.0
200.0
5000.0
12000.0
7000.0
11000.0
9400.0
7300.0
15000.0
12000.0
8500.0
8200.0
9200.0
10000.0
10000.0
12000.0
13000.0
12000.0
10000.0
9600.0
8700.0
12000.0
11000.0
10000.0
7000.0
8100.0
8100.0
4500.0
9700.0
9200.0
IRON
C12
-------
TABLE 9 DETROIT 1982 METALS SUMMARY (mg/kg)
MEAN
STD DEV
SUM
MINIMUM MAXIMUM
METAL
CD
CR
HG
NI
ZN
AG
B
CU
BA
CA
K
MG
NA
FE
BE
CO
PB
LI
MN
MO
SN
SR
V
Y
* Mean values for 10 metals, for which USEPA 1977 Guidelines exist,
exceed guidelines for heavily polluted.
28
28
27
28
28
28
28
28
28
28
28
27
28
28
28
28
28
28
28
28
28
28
28
28
11.118*
203.207*
1.159*
105.714*
891.286*
1.496
12.543
159.143*
194.536*
53428.571
1203.571
15907.143
332.143
38392.857*
0.964
10.818
334.786*
21.750
749.286*
5.718
22.779
99.500
25.143
8.918
18.029
189.189
0.952
79.941
783.299
1.718
4.543
135.142
114.708
18470.053
419.419
2730.612
289.384
19846.334
2.387
2.750
218.247
4.248
494.705
3.801
16.050
51.624
6.468
1.285
311.3
5689.8
31.3
2960.0
24956.0
41.9
351.2
4456.0
5447.0
1496000.0
33700.0
445400.0
9300.0
1075000.0
27.0
302.9
9374.0
609.0
20980.0
160.1
637.8
2786.0
704.0
249.7
0.2
9.8
0.2
15.0
76.0
0.3
8.0
17.0
36.0
28000.0
0
9400.0
100.0
10000.0
0.1
4.7
21.0
13.0
160.0
1.0
4.0
25.0
12.0
5.6
96.0
680.0
3.6
300.0
3500.0
5.9
27.0
720.0
500.0
92000.0
2000.0
22000.0
1600.0
89000.0
9.8
17.0
810.0
28.0
2800.0
16.0
62.0
230.0
40.0
12.0
C13
-------
TABLE 10 SUMMARY TABLE (ug/kg)
STATION #
TOTAL
PAH's
TOTAL
DDT & -
METABO
LITES
TOTAL
PCB's
DTR82-01
DTR82-03
DTR82-05A
DTR82-08
DTR82-13
DTR82-19
ROR82-07
ROR82-Ofi
ROR82-02
DTR82-22
DTR82-23
DTR82-25
DTR82-26
DTR82-27
DTR82-52
DTR82-53
DTR82-29
DTR82-30
DTR82-32
DTR82-38
DTR82-56
DTR82-49
DTR82-43A
DTR82-45
DTR82-48
HUR82-02
HUR82-01
DTR82-57
MEAN=
5150.0
25820.0
2350.0
80660.0
60700.0
97302.0
60800.0
66000.0
125200.0
70000.0
40300.0
35300.0
39300.0
33600.0
23700.0
8820.0
62800.0
20600.0
60910.0
55800.0
48170.0
44300.0
55770.0
41170.0
32960.0
620.0
1000.0
1150.0
42866.0
373.0
2265.0
122.0
361.0
58.0
116.0
645.0
487.0
308.0
242.0
227.0
16.0
118.0
597.0
30.0
445.0
830.0
54.0
847.0
235.0
341.0
142.0
238.0
79.5
68.0
35.0
360.0
116.0
9133.0
290.0
9897.0
1229.0
5041.0
1546.0
2838.0
5160.0
9726.0
5220.0
322.0
7486.0
1410.0
1177.0
3693.0
7963.0
11329.0
13870.0
9173.0
10106.0
3332.0
6326.0
2827.0
22.0
106.0
4618.0
C14
-------
STATION #
TABLE 11(A)
NAPTHA
LENE
POLYNUCLEAR AROMATIC HYDROCARBONS (PAH) IN DETROIT 1982 SEDIMENTS
(UG/KG)
2-METHYL
NAPTHA-
LENE
ACENAPH
THYLENE
ACENAPH
THENE
FLUORENE
ANTHRA
CENE
PHENAN-
THRENE
DTR82-01
DTR82-03
DTR82-05A
DTR82-08
DTR82-13
DTR82-19
ROR82-07
ROR82-06
ROR82-02
DTR82-22
DTR82-23
DTR82-25
DTR82-26
DTR82-27
DTR82-52
DTR82-53
DTR82-29
DTR82-30
DTR82-32
DTR82-38
DTR82-56
DTR82-49
DTR82-43A
DTR82-45
DTR82-48
HUR82-02
HUR82-01
DTR82-57
120.0
980.0
120.0
1430.0
3960.0
11040.0
1300.0
3300.0
6500.0
1100.0
800.0
1400.0
1200.0
1100.0
400.0
180.0
800.0
400.0
7490.0
1500.0
5210.0
1790.0
550.0
900.0
370.0
50.0
100.0
50.0
4610.0
1580.0
1190.0
2780.0
1500.0
1800.0
700.0
300.0
400.0
200.0
600.0
500.0
190.0
700.0
200.0
3960.0
500.0
3240.0
1840.0
300.0
530.0
170.0
40.0
100.0
70.0
510.0
140.0
1340.0
300.0
310.0
200.0
100.0
70.0
90.0
150.0
90.0
40.0
860.0
1570.0
3370.0
900.0
1500.0
2200.0
200.0
100.0
300.0
130.0
400.0
500.0
170.0
110.0
70.0
20.0
160.0
2800.0
60.0
1020.0
2000.0
4420.0
1500.0
1900.0
2310.0
500.0
200.0
300.0
300.0
150.0
400.0
1670.0
800.0
260.0
260.0
90.0
20.0
180.0
1260.0
2140.0
3650.0
1600.0
3940.0
1000.0
700.0
800.0
1300.0
220.0
1300.0
840.0
750.0
680.0
380.0
450.0
880.0
6480.0
460.0
4610.0
8620.0
15320.0
10200.0
8200.0
9800.0
2900.0
1600.0
1700.0
2800.0
3600.0
2000.0
940.0
3700.0
800.0
4410.0
4200.0
1790.0
2710.0
3220.0
1650.0
1020.0
100.0
200.0
120.0
LO
i—t
o
-------
TABLE 1KB) POLYNUCLFAR AROMATIC HYDROCARBONS (PAH) IN DETROIT 1982 SEDIMENTS
(ug/kg)
STATION #
PTR82-01
PTR82-03
DTR82-05A
PTR82-08
PTR8P-13
PTR82-19
ROR82-07
ROR82-06
ROR82-02
DTR82-22
OTR82-23
DTRR2-25
PTR82-26
PTR82-27
DTR82-52
DTR82-53
OTR82-29
PTR82-30
DTR82-32
PTR82-38
OTR8?-56
DTR82-49
DTR82-43A
DTR82-45
DTR82-48
HUR82-02
HUR82-01
PTR82-57
FLIIORAN-
THRENE
1240.0
1860.0
600.0
4100.0
9320.0
13040.0
13600.0
13800.0
11440.0
7200.0
3900.0
3700.0
3900.0
4200.0
6200.0
2390.0
5600.0
1400.0
4300.0
1780.0
2010.0
5080.0
2400.0
2630.0
210.0
300.0
230.0
PYRENE
1010.0
1950.0
500.0
5340.0
8530.0
9440.0
14300.0
16200.0
9350.0
7000.0
4000.0
3600.0
4300.0
3800.0
6000.0
2000.0
7100.0
1500.0
3600.0
1760.0
1980.0
4550.0
2450.0
3030.0
180.0
300.0
200.0
CHRYSENE
XRENZO(A)
ANTHRACENE
1470.0
7140.0
570.0
9210.0
8060.0
5620.0
15600.0
19300.0
14850.0
14900.0
9300.0
8500.0
8700.0
6200.0
8300.0
2620.0
12900.0
4100.0
8000.0
5300.0
6180.0
11600.0
10100.0
8510.0
BENZO
(R/K)FLUO
RANTHENE
13840.0
57900.0
9080.0
20080.0
12600.0
7000.0
7200.0
5700.0
4500.0
11100.0
3900.0
12580.0
11000.0
9270.0
8720.0
10050.0
3510.0
6100.0
RENZO
(GHI)
PERYLENE
106.10.0
2060.0
4120.0
12600.0
4200.0
3100.0
1900.0
2500.0
3900.0
1800.0
7700.0
5400.0
5560.0
5510.0
3900.0
3420.0
1800.0
BENZO
(A)
PYRENE
INDENO
(123-CD)
PYRENE
19230.0
5950.0
10720.0
23670.0
13900.0
7400.0
8000.0
7100.0
5200.0
11900.0
4800.0
16800.0
12200.0
10360.0
9040.0
12120.0
12970.0
7010.00
7060.0
1370.0
3362.0
8150.0
3600.0
1900.0
1500.0
1900.0
3000.0
1700.0
5460.0
3800.0
3900.0
3770.0
3220.0
2400.0
1560.0
480.0
TOTAL
PAH's
5150.0
25820.0
2350.0
80660.0
60700.0
97302.0
60800.0
66000.0
125200.0
70000.0
40300.0
35300.0
39300.0
33600.0
23700.0
8820.0
62800.0
20600.0
60910.0
55800.0
48170.0
44300.0
55770.0
41170.0
32960.0
620.0
1000.0
1150.0
ID
-------
TABLE 12 "HAZARDOUS" PAH's IN DETROIT 1982 SEDIMENTS
(ug/kg)
'STATION #
DTR82-01
DTR82-03
DTRR2-05A
DTR82-08
DTR82-13
DTR82-19
ROR82-07
ROR82-06
ROR82-02
DTR82-22
DTR82-23
DTR82-25
DTR82-26
DTR82-27
DTR82-52
DTR82-53
PTR82-29
DTR82-30
DTR82-32
DTR82-38
DTR82-56
DTR82-49
DTR82-43A
DTR82-45
DTR82-4S
HUR82-02
HURR2-01
PTR82-57
19230.0**
5950.0*
10720.0*
23670.0**
13900.0*
7400.0*
8000.0*
7100.0*
5200.0*
11900.0*
4800.0*
16800.0*
12200.0*
10360.0*
9040.0*
12120.0*
12970.0*
7010.0*
CHRYSENE
&BENZO(A)
ANTHRACENE
1470.0
7140.0
570.0
9210.0
8060.0
5620.0
15600.0
19300.0
14850.0
14900.0
9300.0
8500.0
8700.0
6200.0
8300.0
2620.0
12900.0
4100.0
8000.0
5300.0
6180.0
11600.0
10100.0
8510.0
480.0
INDENO
(123-CD)
PYRENE
7060.0
1370.0
3362.0
8150.0
3600.0
1900.0
1500.0
1900.0
3000.0
1700.0
5460.0
3800.0
3900.0
3770.0
3220.0
2400.0
1560.0
BENZO
(B/K)FLUO
RANTHENE
13840.0
57900.0
9080.0
20080.0
12600.0
7000.0
7200.0
5700.0
4500.0
11100.0
3900.0
12580.0
11000.0
9270.0
8720.0
10050.0
3510.0
6100.0
PHENAN-
THRENE
880.0
6480.0
460.0
4610.0
8620.0
15320.0
10200.0
8200.0
9800.0
2900.0
1600.0
1700.0
2800.0
3600.0
2000.0
940.0
3700.0
800.0
4410.0
4200.0
1790.0
2710.0
3220.0
1650.0
1020.0
100.0
200.0
120.0
2350
13620*
1030
53950*
81900**
44102*
25800*
27500*
76550**
47900*
27200*
25400*
25800*
21400*
10300*
3560
42600*
15300*
39250*
39200*
30620*
30420*
40210*
30630*
24200*
100
200
600
* = >1,000
** = HIGHEST
CONCENTRATIONS
* = >10,000
** = HIGHEST
CONC.
C17
-------
TABLE 13 PCB'S IN DETROIT 1982 SEDIMENTS (ug/kg)
STATION #
DTR82-01
DTR82-03
DTR82-05A
DTR82-08
PTR82-13
DTR82-19
ROR82-07
ROR82-06
ROR82-02
DTR82-22
DTR82-23
DTR82-25
PTR82-26
DTR82-27
DTR82-52
DTR82-53
DTR82-29
DTR82-30
DTR82-32
DTR82-38
DTR82-56
DTR82-49
DTR82-43A
DTR82-45
DTR82-48
HUR82-02
HUR82-01
DTR82-57
PCB-1242 % PCB-1248 % PCB-1254 % PCB-1260 %
7
21
39
63
50
26
30
79.0
75.0
956.0 13
253.0
563.0
7
7
58.0
5034.0
109.0
2612.0
154.0
940.0
552.0
911.0
1150.0
6940.0
605.0
199.0
3630.0
363.0
435.0
2280.0
4950.0
6562.0
6397.0
2943.0
4082.0
871.0
2507.0
708.0
22.0
50
55
38
26
13
19
36
32
22
71
12
62
48
26
37
62
62
58
46
32
40
26
39
25
100
58.0
3482.0
119.0
3467.0
294.0
1584.0
593.0
1072.0
1620.0
987.0
1930.0
123.0
2900.0
492.0
411.0
1160.0
2450.0
2863.0
3638.0
2284.0
3076.0
994.0
2194.0
1012.0
50
38
41
35
24
31
38
38
31
10
37
38
39
35
35
31
30
25
26
25
30
29
34
36
617.0
62.0
3818.0
781.0
2517.0
401.0
855.0
2390.0
1720.0
2610.0
555.0
331.0
1904.0
3835.0
3946.0
2948.0
1467.0
1625.0
1107.0
46
18
50
39
28
17
28
43
29
44
25
39
62.0 58
44.0
42
TOTAL
PCB's
116.0
9133.0
290.0
9897.0
1229.0
5041.0
1546.0
2838.0
5160.0
9726.0
5220.0
322.0
7486.0
1410.0
1177.0
3693.0
7963.0
11329.0*
13870.0*
9173.0
10106.0*
3332.0
6326.0
2827.0
22.0
106.0
TOTALS
AVERAGE
LEVELS
1926
68
55076
1967
388*7
1387
33489
1196
129338
4618
*=Pol1uted (USEPA 1977 Guidelines)
C18
-------
TABLE 14 DDT A METABOLITES IN DETROIT 1982 SEDIMENTS (ug/kg)
;TATION
p,p'DDT p,p'DDD p.p'DDE
o,p'DDT o,p'DDD o.p'DDE
TOTAL
DDT &
METABO-
LITES
)TR82-01
ITR82-03
>TR82-05A
[TR82-08
ITR82-13
|)TR82-19
10R82-07
!OR82-06
[OR82-02
JTR82-22
1TR82-23
[1TR82-25
JTR82-26
(VTR82-27
1TR82-52
i)TR82-53
>TR82-29
!rTR82-30
i)TR82-32
)TR82-38
DTR82-56
1TR82-49
)TR82-43A
3TR82-45
LITR82-48
HUR82-02
HUR82-01
DTR82-57
14.0
95.0
4.0
15.0
23.0
39.0
107.0
180.0
111.0
70.0
44.0
37.0
13.0
19.0
212.0
1255.0
26.0
177.0
30.0
37.0
205.0
63.0
49.0
73.0
62.0
60.0
158.0
166.0
324.0
8.0
268.0
66.0
157.0
63.0
94.0
35.0
27.0
19.0
43.0
262.0
89.0
67.0
5.0
9.0
37.0
23.0
25.0
28.0
24.0
47.0
28.0
61.0
202.0
21.0
57.0
46.0
94.0
34.0
122.0
16.0
18.0
10.0
9.0
52.0
18.0
18.0
37.0
63.0
38.0
42.0
18.0
431.0
6.0
46.0
309.0
3.0
32.0
13.0
77.0
158.0
110.0
8.0
7.0
16.0
50.0
65.0
173.0
11.0
9.0
37.0
32.0
22.0
17.5
49.0
292.0
52.0
182.0
66.0
86.0
34.0
263.0
2.0
153.0
131.0
7.0
80.0
114.0
53.0
5.0
4.0
3.0
3.0
373.0
2265.0
122.0
361.0
58.0
116.0
645.0
487.0
308.0
242.0
227.0
16.0
118.0
597.0
30.0
445.0
830.0
54.0
847.0
235.0
341.0
142.0
238.0
79.5
68.0
35.0
C19
-------
TABLE 15 PESTICIDES IN DETROIT 1982 SEDIMENTS (ug/kg)
STATION # BETA BHC
ENDOSULFAN 6AM1A- OXY-
-II DCPA DIELDRIN CHLORDANE CHLORDANE
HEPTACHLOR- TRI-
EPOXIDE FLURALIf
DTR82-01
PTR82-03
DTR82-05A
DTR82-08
DTR82-13
PTRS2-19
ROR82-07
ROR82-06
ROR82-02
DTR82-22
DTR82-23
DTR82-25
PTR82-26
DTR82-27
DTR82-52
DTR82-53
DTR82-29
DTR82-30
DTR82-32
PTR82-38
DTR82-56
DTR82-49
DTR82-43A
DTR82-45
DTR82-48
HUR82-02
HUR82-01
PTR82-57
29.0
170.0
15.0
74.0
20.0
39.0
195.0
83.0
160.0
6.0
6.0
1.0
7.0
12.0
10.0
14.0
10.0
14.0
14.0
11.0
4.0
24.0
145.0
17.0
95.0
63.0
39.0
21.0
47.0
13.0
149.0
64.0
10.0
10.0
90.0
45.0
14.0
39.0
21.0
6.0
81.0
44.0
87.0
61.0
106.0
74.0
25.0
18.0
9.0
C20
-------
TABLE lfi(A) VOLATILE ORGANICS IN DETROIT 1982 SEDIMENTS (ug/kg)
STATION #
DTR82-01
DTR82-03
DTR82-n5A
DTR82-08
DTR82-13
DTR82-19
ROR82-07
ROR82-06
ROR82-02
DTR82-22
DTR82-23
DTR82-25
DTR82-26
DTR82-27
DTR82-52
DTR82-53
DTR82-29
DTR82-30
DTR82-32
DTR82-38
DTR82-56
DTR82-49
DTR82-43A
DTR82-45
DTRS2-48
HUR82-02
HUR82-01
DTR82-57
1,1,2,2-
TETRA-
CHLORO-
ETHANE
10.0
16.0
14.0
27.0
20.0
13.0
21.0
TETRA-
CHLORO- METHYL
ETHENE BENZENE
3.0
214.0
107.0
5.0
2.0
4.0
6.0
2.0 4.0
6.0
3.0
4.0
6.0
42.0
4.0
13.0
2.0
CHLORO- ETHYL
BENZENE BENZENE
27.0
3.0
201.0
3.0
2.0
3.0
2.0
3.0
3.0 3.0
12.0
1.0 8.0
6.0
8.0
6.0
2.0 3.0
1.3-
DIMETHYL
BENZENE
8.0
181.0
4.0
2.0
3.0
24.0
10.0
1,2&1,4
DIMETHYL
BENZENE
51.0
17.0
9.0
170.0
15.0
8.0
4.0
5.0
18.0
29.0
21.0
3.0
C21
-------
TABLE 16(B) VOLATILE ORRANICS IN DETROIT 1982 SEDIMENTS (ug/kg)
STATION *
DICHLORO
METHANE
TRICHLRO CHLORO-
METHANE FORM
1,2-DI
CHLORO-
PROPANE
TRI
CHLORO
ETHENE
BENZENE
DTR82-01
DTR82-03
DTR82-05A
DTR82-08
DTR82-13
DTR82-19
ROR82-07
ROR82-06
ROR82-02
DTR82-22
DTR82-23
DTR82-25
DTR82-26
nTR82-27
DTR82-52
DTR82-53
DTR82-29
RTR82-30
DTR82-32
DTR82-38
DTR82-56
DTR82-49
DTR82-43A
DTR82-45
DTR82-48
HUR82-02
HUR82-01
DTR82-57
4.0
4.0
6.0
5.0
4.0
6.0
5.0
7.0
6.0
6.0
59.0
60.0
91.0
5.0
5.0
16.0
20.0
11.0
10.0
10.0
10.0
4.0
3.0
6.0
3.0
1.0
10.0
7.0
23.0
22.0
5.0
5.0
6.0
6.0
19.0
2.0
17.0
4.0
6.0
10.0
4.0
27.0
3.0
26.0
22.0
32.0
3.0
4.0
5.0
41.0
50.0
6.0
29.0
28.0
20.0
26.0
27.0
20.0
14.0
21.0
17.0
3.0
C22
-------
TABLE 17 PHENOLS IN DETROIT 1982 SEDIMENTS (ug/kg)
(STATION
PHENOL
P-CRESOL
2,4-
DIMETHYL
PHENOL
DTR82-01
OTR82-03
DTR82-05A
DTR82-OS
DTR82-13
DTR82-19
ROR82-07
ROR82-06
ROR8P-02
DTR82-22
r>TRS2-?3
DTR82-25
DTR82-26
DTR82-27
DTR82-52
DTR82-53
DTR82-29
DTR82-30
DTR82-32
DTR82-38
DTR82-56
DTR82-49
PTR82-43A
DTR82-45
DTR82-48
HUR82-02
HUR82-01
DTR82-57
580.0
90.0
480.0
110.0
370.0
1100.0
470.0
80.0
1490.0
9500.0
2460.0
320.0
650.0
100.0
30.0
1980.0
630.0
160.0
1390.0
1500.0
600.0
490.0
800.0
200.0
190.0
500.0
4140.0
9910.0
3200.0
280.0
750.0
90.0
20.0
80.0
530.0
25100.0
20400.0
160.0
700.0
150.0
C23
-------
TABLE 1R SIIBSTirilTEn BENZENES, SUBSTITUTED CYCLIC KETONES, AND POLYCYCLIC AROMATICS
IN DETROIT 1982 SEDIMENTS (ug/kg)
STATION #
DTR82-01
OTR82-03
DTR82-05A
RTR82-08
DTR82-13
DTRR2-19
RORR2-07
RORR?-Ofi
ROR82-02
IUR82-2?
IVTR82-23
(1TIW-25
IIIR 82-26
(1TR82-27
DTR8Z-52
DTRR2-53
DTR82-29
DTR82-30
DTR82-32
RTRR2-38
nTR82-56
HTR82-A9
HTR82-43A
DTR82-45
OTR82-4R
HI IR 82-02
HUR82-01
OTR82-57
i,3-ni 1,4-Di
CHLORO CHLORO
ANILINE BENZENE BENZENE
940.0
300.0
50.0
150.0
500.0
?00.0
130.0
100.0
70.0
100.0
80.0 350.0
200.0
470.0
160.0 190.0
70.0 110.0
1,2-01 1,2,4-TRI HEXA-
CHLORO CHLORO CHLORO-
BENZENE BENZENE BENZENE
21.0
2.0
14.0
3.0
15.0
500.0 30.0
14.0
8.0
9.0
14.0
O.OT
33.0
12.0
17.0
5.0
9.0
180.0 18.0
106.0
520.0 92.0
110.0 110.0 46.0
71.0
60.0 98.0
35.0
4-CHLORO DIBENZO ISO-
ANILINE FURAN PHORONE
50.0
290.0
1150.0
3620.0
300.0 900.0
400.0
1910.0
200.0
100.0
70.0
200.0
1000.0
160.0
200.0
70.0
DI-N-
niETHYL BUTYL
PHTHALATE PHTHALATE
2540
5690
540
5470
320
2320
2700
4900
780
4200
1350
930
1300
660
140
170
20.0 520
2000
30.0 1730
BIS
(2-EH)
PHTHALATE
490
15640
650
11280
8900
5870
33000
2100
4790
23300
16300
14300
28000
12000
4540
47100
4900
11390
25500
30220
21310
3120
5430
1580
460
1000
640
CVJ
O
O.OT
T=Valne reported 1s less than criteria of detection.
-------
Figure1
Detroit Area Industry
(Reprinted by Permission from Thornley and Hamdy, 1984)
OMroit
t»u Siwimg Ltd.
amid »»«'«9«t«» Lid.
Dl
-------
Figure 2
Bedrock Surface Topography
Reprinted From Mozola, 1969
_ Rl3E
f~££^ W^^B&WMB^J
TOPOGRAPHY OF THE BEDROCK SURFACE
OF WAYNE COUNTY, MICHIGAN
by
ANDREW J MOZOLA
Wayne Stole Umv«rsity-l967
Scot. M M.I.,
CONTOUR INTERVAL-fS FEET
D2
-------
Figure 3
Detroit River Study Area
(Reprinted by Permission from Thornley and Hamdy, 1984)
LAKE, ST. CLAIR
MICHIGAN
ERIE
N
MILES
D3
-------
Figure 4
Hydrographs
(Reprinted from Wisler et a I, 1952)
] 0
Hydrograph of Huron River at Barton for a median year.
Bydrograph of River Rouge at Detroit for a median year.
D4
-------
FIGURE 5
STATUTE MILE
•A Vi 1 2 3 4
LAKE ERIE
DETROIT, MICHIGAN
Sediment Sampling Sites
October 26-28.1982
Great Lakes National Program Office
USEPA Chicago, IL.
D5
-------
FIGURE 6
HURON RIVER, MICHIGAN
Sediment Sampling Sites
. October 28,1982
Great Lakes National Program Office
USEPA Chicago, 1L.
•Samples Analysed
06
-------
Figure 7
Detroit Area Municipal and Combined Storm Sewer Facilities
(Reprinted by Permission from Comba and Kaiser. 1985)
MIC HIG AN
CONNERS
CHEEK.
1^
« /
OUTFALL. /
\U
^4 m rre^i i •
RWERSTP
WYANDOTTE
WYANDOTTE STP OUTFALL
RIVERV1EW
GBRALTAR
5km
•STP SEVWVGE TREATMENT PLANT OUTFALLS
— COMBINED SEWER OVERFUDWS
• SEWNGE TREATMENT PLANT LOCATIONS
A HYDRO FACNJTIES
E3 SPOIL AREA
«MUNICIF«M. WKTER INTAKES
D7
-------
Fyart 8 TOTAL VOLA TILE SOLIDS IN DETROIT SEDIMENTS
Figurf S OIL AND GREASE IN DETROIT SEDIMENTS
I I
IISFPA!
Gl'inri
ill«E5l
I I
ST«TIO«S|ni 03 SA|Ofl 13119 R7 Rfi R?
»EIIF l.|F»TO-l ROIIGF R.
I I «IT|
?? ?3 75 7f ?
ROIKI R. TO
1 53 ?9 30)3? 38 56 49|43 '? 73 n If. 77K7 51 ?9 30132 38 56 »9|43 45 48
ROLICF R. TO I EfORSE R. | NORTHERN (SOUTHERN
ECORSt ».| | TRENTON CHANNEL
Figure 10 COD IN DETROIT SEDIMENTS
Figure 11 TKN IN DETROIT SEDIMENTS
H
r.
/
K
R
-
-
?4finoru-
-
-
-
-
»-
.
.
-
W?noo--
-
--
_
,
_
.
IWOO--
-
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-
-
-
_
8»f¥MW-
t
HICK
W
1977
IISFM
rapine
If)
I
-
IIIEM
L
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w 3inon—
1
*
STATIOH5I01 03 SA|08
1
iELlF
. nETi
*
1
T
0
T
A
* L
1
1
1
.
3|19 R7 Rfi R?
1 OIT
ROtlfiF R.
1
•
• *
*
• K
J
F
L
n
A
H
L
• f
I
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9
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G
t
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K
R
HIGH
Hfih
T57T
• US EPA
* r-uirt
LI NFS
* L(TU
i
>? 23 25 76 27|52 53 29 30|3? 38 66 49|43 45 48|H? HI 57| ?T
ROUGE R. TO
ECORSE R.
ECORSE ft.
NORTtCRN {SOUTtCRN HURON R.I
TRENTON CHANNEL |
86f>0-
"I
„
7010—
_
_
_
„
__
_
„
.
5*?n--
_
.
.
_
.
_
WO--
ft
.
.
_
.
??10—
-
I
.
—
.
"
6«0-|
*
•UIOIK n\ 03 S*|OR 13j
8ELLF
-(
»
0 R7 R6 R?
ROUGE
R
1 OITl
*
*
• • •
•
•
•
•
-^
*
* •
— f ,
i
?? ?3 ?5 76 77 5? 53 79 3013? 38 56 49(43 45 48 tf >
ROUHE ft. TO ECORSE R. | NORTtCRN (SOUTHERN HIRO
erMSf R. | TRENTON CHANNEL
D8
-------
Figurt 12 AMMONIA IN DETROIT SEDIMENTS
Fyurt 13 PHOSPHORUS IN DETROIT SEDIMENTS
I*
ES
IS|01 03 5A[08 H Ifl R7 R$ R?
IBEtLF I. WTR- ROIIC.E R.
0!T|
?? 23 25 26 27|52 53 29 30|32 3S 56 49|43 45 48|H2 HI 571
ROIIOE R. TO ECORSF R. | NORTHERN ISOUTHIRNIHURON R.j
ECDR5ER.) | TRENTON CHMIKL | |
5430- -
P
0
P 41M)--
H
n
R
II
s
K 2890--
r,
iwn—
_
_
1)977 1 HJf.H
Ir.nint
IllNE";
KIP
LOU
320 - *
1
1
STUTIONSIOl 03 5A|OB 13|
I«FL
1
F r.|nrT»-|
1 ""I
*
1
1
1
1
<
.
• *
9 R7 R6 R2I22 23 25
KCIUCf
8
I POJKE ff.
*
^
»
»
»
*
» ?7|5? S3 ?9 30132 38 SA 49|43 45 4
TO
fC
I CCOR1E R. |
ORSF R.) KKTWR1 jSOUTtCR
| TRENTON CHANNEL
* *
*
8 H? HI 5
N WRON R
Figure 14 CYANIDE IN DETROIT SEDIMENTS
Figure IS LEAD IN DETROIT SEDIMENTS
7T|
I\K
NESP
1077 JHIR
ciunt
iLUFSILnu 21.0-
ST»T!0«S|01 03 5A|l)fl I3|I9 R7 R
IBEUF i.|nETn-| ROnre
I I orTJ
R2|7? n K ?6 ?7|
R. | ROIKE R. TO i
| KOKSE e. |
53 29 30(32 3S 56 49|43 45 48
ECORSF R. NORTICRN [SOUTHERN
TBEHTON CWKNEL
K2 HI 57
HURON R.
ST»TIOIK|01 03 5A|OB 13|19 87 R6 R2|22 23 25 2« ?7|52 53 29 30|3? 3« 56 49|43 45 48|H2 Ml 57|
IHFLIE i.|ncT»-| ROIIK R. ROUGC R. TO fcnssER.i «*THre« (SOUTHEMImam ». I
I I OIT| | ECWSE R. I TRENTON CWNNEL I I
D9
-------
Figure 16 ZINC IN DETROIT SEDIMENTS
Figure 17 IRON IN DETROIT SEDIMENTS
Usn.n..
;
761.0—
:
rRTnwr.li
IIISEMIMTOI
.
«
ir.nltf ILOU 7f.o--' I
IL1NESI
^TATIOIKlOl 03 5A|Of nil" R7 R6 R?l
IRFIIF i.|ntTR-l Rnunr R. I
1 1 on 1
.
RO
•
•
H r
3 ?5 7ft 77
Iff R. Ttl
FrDRSE R.
'
S? S3 79 3(1 1
ECHRSF R.|
1
1 •
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i t ! * 1
NOftTHfRN jSnHTK»»!KiRf>N R.
TKFNTON tVWNNLL |
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(niurf I
ILlllESi
574on.n--
4i«no.n.:
-
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Hlf.H
WTfi I '
:
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i
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«
1
STATIOHM"! "3 5«!OR 13119 R7 R6 R?|?Z 73 ?5 ?fi ?7I5? 53 29 30
IBEUF i.|nfTp.| KOIKSE R. I ROUGE B. to 1 ECORSE «.
I | OIT| | ECORSF R.i
32 3R 5fi 49M3 45 48
HORTtCRN |SOUT>CRN
TRENTON CHUBNEL
H2 HI 57
HURON R.
Figure 18 NICKEL IN DETROIT SEDIMENTS
Figure 19 MANGANESE IN DETROIT SEDIMENTS
Hir.H
11971 |«Sfi
IIKEP/M
Riiirl
ILIIIESI
LOW 15.0-'
I I
IOl 03 5A OB 13|19 R7 Rft R2 ZZ 23 25 ?6 27 52 53 29 30 32 38 56 49|«3 45 48
IRFLIF 1. ncTR.| ROUGE R. ROUGf R. TO ECORSF. R. MttTICRN JSOUTICRN
OIT ECORSE R. TOEKIOh CHMmEL
a HI 57
HWON R.
I1»7T| HIGH
jlKFRftj »*Mi
r-iiiiri
lIUFSi
TOT-
I !
I I
STATlOJRIni 03 5A|OR 13119 R7 R6 R2I27 73 75 ?S 77|52 53 29 30132 3R 5S 49143 45 48
IBFIIF I.IHFTR-I torn R. I ROUGE R. TP ecoR^c «.| «™THERH ISOUTWRN
I j OIT| | ECORSE R. I I TRFNTO" CHUNBEL
DID
-------
Figurt 20 CADMIUM IN DETROIT SEDIMENTS
Fifun 21 CHROMIUM W DETROIT SEDIMENTS
7C.K-
C
A
n
n
' 1 57.7—
III
H
G
1 f
1 «
! r-
3».1—
;
1 -"-
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1 I nni
546. n—
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Figure 22 BARIUM IN DETROIT SEDIMENTS
Figure 23 COPPER IN DETROIT SEDIMENTS
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f igur* 24 MERCURY IN DETROIT SEDIMENTS
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Figure 26 BORON IN DETROIT SEDIMENTS
Figure 27 BERRYLIUM IN DETROIT SEDIMENTS
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D12
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figure 28 COBALT m DETROIT SEDIMENTS
figure 29 LITHIUM M DETROIT SEDIMENTS
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figure 30 MOLYBDENUM IN DETROIT SEDIMENTS
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figure 3t TIN IN DETROIT SEDIMENTS
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D13
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Figurf 32 STRONTIUM IN DETROIT SEDIMENTS
Figure 33 VANADIUM IN DETROIT SEDIMENTS
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Figure 34 CALCIUM IN DETROIT SEDIMENTS
Figure 35 POTASSIUM IN DETROIT SEDIMENTS
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D14
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fifun 36 SODIUM IN DETROIT SEDIMENTS
Figun37 ALUMINUM IN DETROIT SEDIMENTS
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Figure 39 2 -METHYL NAPHTHALENE IN DETROIT SEDIMENTS
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Figure 4O FLUORENE IN DETROIT SEDIMENTS
Figure 41 ANTHRACENE IN DETROIT SEDIMENTS
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Figure 42 PHENANTHRENE IN DETROIT SEDIMENTS
Figure 43 FLUORANTHENE IN DETROIT SEDIMENTS
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D16
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Figun44 PYRENE IN DETROIT SEDIMENTS
Figun 46 CHRYSENE AND BENZOtA) ANTHRACENE IN DETROIT SEDIMENTS
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Figure 46 BENZCXGHIPERYLENE IN DETROIT SEDIMENTS
Figure 47 BENZOIAIPYRENE IN DETROIT SEDIMENTS
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D17
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Figun 48 PCB 1242 IN DETROIT SEDIMENTS
Figun 43 PCB 1248 IN DETROIT SEDIMENTS
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-------
figun 62 GAMMA CHLORDANC IN DETROIT SEDIMENTS
Figurt 53 KTA BHC IN DETROIT SEDIMENTS
r.
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Figure 54 DICHL OROMETHANE IN DETROIT SEDIMENTS
Figure 55 TRICHL OROETHENE IN DETROIT SEDIMENTS
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Figure 56 PHENOL IN DETROIT SEDIMENTS
Figure 57 PARA-CRESOL IN DETROIT SEDIMENTS
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f/pure 58 HEXACHLOROBENZENE IN DETROIT SEDIMENTS
Figure 59 DIBENZOFURAN IN DETROIT SEDIMENTS
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D20
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Figure 60 BIS 2 ETHYL -HEXYL PHTHALA TE IN DETROIT SEDIMENTS
j 43 4b aniH? HI S7i
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D21
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TECHNICAL REPORT DATA
(titdi rc-J lis*i-u, tun, : o>> l'>i ret in,, be /i". carr.firii'if
) fitPORT NC 2 ... — ,.
EPA-905/4-003
4. TITLE ANDSUBTTLE
1982 Detroit, Michigan Area Sediment Survey
7. AUTHOR(S)
Pranas E. Pranckevicius
9 PERFORMING ORGANIZATION NAME AND ADDRESS
Great Lakes National Program Office
U.S. Environmental Protection Agency
230 South Dearborn
Chicago, IL 60604
12. SPONSORING AGENCY NAME AND ADDRESS
Great Lakes National Program Office
U.S. Environmental Protection Agency
230 South Dearborn
Chicago, IL 50604
3 RECIPIENT'S ACCtSS'ON-NO
5 REPORT DATE
July 1987
6. PERFORMING ORGANIZATION CODE
5GL
B. PERFORMING ORGANIZATION REPORT NO.
GLNPO Report No. 87-11
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
13. TYPE OF REPORT AND PERIOD COVERED
Sediment 1982
14. SPONSORING AGENCY CODE
Great Lakes National Program
Office - USEPA - Region V
17.
Twenty-eight sediment grab samples from the western bank of the Detroit River and
three of its tributaries were chemically analyzed. Sampling sites were chosen to
find worst-case conditions. High levels of conventional pollutants and metals were
found throughout most of the study area. Hydrophobic organic contaminants found in
a wide range of concentrations included: Polynuclear aromatic hydrocarbons,
Polychlorinated biphenyls, various pesticides, and volatile organic compounds.
Contaminant distributions suggest recent inputs from local sources. Highest
contaminant levels were found in the Rouge River, the northern Trenton Channel and
Conners Creek in the Belle Isle Area. The City of Detroit Wastewater Treatment
Plant, combined sewer overflows, local steel and chemical industry and oil
refineries are implicated as likely sources. Several contaminants including
volatile organics, PCBs and hexachlorobenzene, seem to have major upstream sources,
perhaps in Lake St. Clair or the St. Clair River.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Sediment, conventional pollutants,
metals, organic contaminants,
Detroit, Michigan
DISTRIBUTION STATEMENT
Document is available through the
National Technical Information Service
Springfield, VA 22161
EPA Form 2220-1 (9-73)
b.lDENTIFIERS/OPEN ENDED TERMS
Detroit River
Rouge River
Huron River
Conners Creek
Monguogon Creek
Trenton Channel
19. SECURITY CLASS (This Report)
Unclassified
20. SECURITY CLASS (Thispage)
Unclassified
c. COSATI Field/Group
21
NO. OF PAGES
116
22. PRICE
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