&EPA
United States
Environmental Protection
Agency
Great Lakes National
Program Office
536 South Clark Street
Chicago, Illinois 60605
EPA 905/4-84-003
Great Lakes National
Program Office
Harbor Sediment Program
Lake Superior 1981:
Ashland, Wisconsin,
Black River, Michigan,
L'anse, Michigan
-------
EPA 905/4-84-0003
April
-4
GREAT LAKES NATIONAL PROGRAM OFFICE
HARBOR SEDIMENT PROGRAM
LAKE SUPERIOR 1981 :
ASHLAND, WISCONSIN
BLACK RIVER, MICHIGAN
L'ANSE, MICHIGAN
Anthony G. Kizlauskas
David C. Rockwell
Roger E. Claff
for
U.S. ENVIRONMENTAL PROTECTION AGENCY
GREAT LAKES NATIONAL PROGRAM OFFICE
536 SOUTH CLARK STREET
CHICAGO, ILLINOIS 60605
-------
DISCLAIMER
This report has been reviewed by the Great Lakes National Program Office,
U.S. 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 commerical products constitute endorsement or recommendation for use.
-------
Table of Contents
Foreword
Tables
Figures
Acknowledgements
Introduction
Background
Sampling Methodology
Sampling Equipment
Analytical Methodology
Results: Ashland, Wisconsin
Black River, Michigan
L'Anse, Michigan
References
iii
iv
V
vi
1
1
2
4
4
9
21
32
43
Appendix A - Guidelines for the Pollutional Classification
of Great Lakes Harbor Sediments A-l
11
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FOREWORD
The Great Lakes National Program Uffice (GLNPO) of the United States Environ-
mental 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 GLNPU 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
U.S. actions in fulfillment of the Great Lakes Water Quality Agreement of
1978 between Canada and the United States of America.
iii
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Tables
1. Field Observations: Ashland, Wisconsin, May 21-22, 1981. 12
2. Sediment Concentrations of Some Conventional Pollutants and Metals:
Ashland, Wisconsin, May 21-22, 1981. 13
3. Sediment Concentrations of PCBs and Pesticides by the GC/EC Method:
Ashland, Wisconsin, May 21-22, 1981. 14
4. Organic Compounds Sought in Sediments by the GC/MS Method and Maximum
Detection Limits: Ashland, Wisconsin, May 21-22, 1981. 15
5. Organic Compounds Identified in Sediments by the GC/MS Method:
Ashland, Wisconsin, May 21-22, 1981. 19
6. Organic Compounds Tentatively Identified in Sediments by the GC/MS
Method: Ashland, Wisconsin, May 21-22, 1981. 20
7. Field Observations: Black River, Michigan, May 22, 1981. 23
8. Sediment Concentrations of Some Conventional Pollutants and Metals:
Black Kiver, Michigan, May 22, 1981. 24
9. Sediment Concentrations of PCBs and Pesticides by the GC/EC Method:
Black River, Michigan, May 22, 1981. 25
10. Organic Compounds Sought in Sediments by the GC/MS Method and Maximum
Detection Limits: Black River, Michigan, May 22, 1981. 26
11. Organic Compounds Identified in Sediments by the GC/MS Method:
Black River, Michigan, May 22, 1981. 30
12. Organic Compounds Tentatively Identified in Sediments by the GC/MS
Method: Black River, Michigan, May 22, 1981. 31
13. Field Observations: L'Anse, Michigan, May 23, 1981. 34
14. Sediment Concentrations of Some Conventional Pollutants and Metals:
L'Anse, Michigan, May 23, 1981. 35
15. Sediment Concentrations of PCBs and Pesticides by the GC/EC Method:
L'Anse, Michigan, May 23, 1981. 36
16. Organic Compounds Sought in Sediments by the GC/MS Method and Maximum
Detection Limits: L'Anse, Michigan, May 23, 1981. 37
17. Organic Compounds Identified in Sediments by the GC/MS Method:
L'Anse, Michigan, May 23, 1981. 41
18. Organic Compounds Tentatively Identified in Sediments by the GC/MS
Method: L'Anse, Michigan, May 23, 1981. 42
IV
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Figures
1. Ashland, Wisconsin Sediment Sampling Sites, May 21-22, 1981. 11
2. Black River, Michigan Sediment Sampling Sites, May 22, 1981. 22
3. L'Anse, Michigan Sediment Sampling Sites, May 23, 1981. 33
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Acknowledgements
A great deal of credit goes to our colleagues within the Great Lakes National
Program Office for support in planning, site selection, collection of sediments
compilation of data, data management, and interpretation of results. In parti-
cular David DeVault, Rossetta McPherson, Michael Pandya and Stanley Witt
deserve special mention for their efforts in this project.
We want to thank Clifford Kisley, dr., and Vacys Saulys for their reviews
of the manuscript.
The chemical analysis of the sediments has been undertaken by Central
Regional Laboratory, USEPA Region V, via contract to BIONETICS. Ms. Andrea
Jirka and Ms. Marcia Kuehl provided the information on analytical methodology.
Ms. Gaynell Whatley is to be commended for her typing of the report and the
extensive tables.
VI
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Introduction
This report contains sediment chemistry data from three areas on Lake Superior
that were sampled in 1981 under the Great Lakes National Program Office (GLNPO)
Harbor Sediment Program: Ashland, Wisconsin; Black River, Michigan; and L'Anse,
Michigan.
Background
Harbor Sediment Program
Toxic substances are being introduced into the environment from many sources.
Secondary compounds from these toxicants are often formed in the environment.
Some of these secondary compounds are more hazardous than the primary chemicals
from which they came, (e.g., dioxins vs. pentachlorophenol, respectively).
Sediments serve as a sink as well as a potential source for toxic and con-
ventional pollutants. Even if discharges of pollutants are completely
eliminated, contaminated sediments can serve as a source of pollution to
aquatic life, the Great Lakes, and the populations using the water bodies
for drinking water supplies for many years to come. If one names the toxic
substance problem areas around the Great Lakes: Waukegan, Illinois; Indiana
Harbor Canal, Grand Calumet River, Indiana; Ashtabula, Ohio; Saginaw River
and Bay, Michigan; Sheboygan River, Green Bay, and Milwaukee, Wisconsin;
Buffalo and Niagara, New York; the "problem" is invariably linked with
toxics in the sediments.
Some 10 million cubic meters of sediments are dredged annually to maintain
navigation in Great Lakes' ports. Many of these ports contain sediment con-
taminated with toxic substances. Environmentally safe dredging and disposal
is necessary to protect the lakes, wildlife, and the public while maintaining
the economic viability of water borne commerce.
1
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Due to the relatively recent identification of in-place pollutants as major
remaining sources of contaminants and availability of the analytical
capability to allow the measurement of toxic organics, only a very limited
and disjointed data base exists for organic contaminant levels in
sediments. To fill the void, GLNPO is in the second year of a multi-year
effort to determine the level of toxic substances in Great Lakes' river and
harbor sediments. Sampling priorities are being determined by examining fish
flesh contaminant data, locations of likely industrial sources, and by review
of USEPA and other agency data.
Nineteen surveys were completed in 1981 including the Buffalo and Niagara
River area. This report summarizes the results from the three surveys done
on Lake Superior.
The information generated by this program will be used in making regulatory
decisions on dredging and disposal and to identify environmental "hot spots"
requiring further remedial activity including identification and control
of sources. Chemicals monitored in the sediments will form a new information
base for the Great Lakes. Selected samples will be scanned for organics and
metals using best available methods. The organic scans involve acid,
base, and neutral extractions of volatile and non-volatile substances and
identification and quantification using gas chromatography mass-spectral
technology (GC/MS). Quantification is routinely done by gas chromatograph
electron capture (GC/EC) technology for PCBs and some 30 pesticides.
Sampling Methodology
Sediment samples were collected in the manner described in the Methods Manual
for Bottom Sediment Sample Collection (USEPA, 1984). This manual provides
detailed procedures for survey planning, sample collection, document pre-
paration and quality assurance for sediment sampling surveys.
-------
Each site survey is designed by determining and Plotting on a large scale
map the location of sewage treatment plant discharges, combined sewer dis-
charges (particulary those carrying industrial waste), industrial discharges,
and any other feature that might result in contaminated sediments. To this
is added any data on sedimentation patterns that may exist from dredging
records, and existing data on sediment quality. This information is used
to identify locations where contaminated sediments are most likely to be
found. Because sample sites are chosen to find worst-case conditions, the
analytical data do not necessarily represent the ambient sediment contaminant
levels in the area.
Two categories of sampling sites are selected. Primary sites are sites that
are most likely to be contaminated and are scanned and run for specific compounds
which are known to be used in the area or have been found in fish from the
area. Secondary sites are sites which will be run if the primary sites indicate
significant contamination exists and will be used to define the extent of the
contamination. Secondary samples would only be analyzed for the specific compounds
indicated as significant contaminants at primary sites.
In general, the finer and more polluted sediments will deposit along the edges
of a navigation channel, on the inside edge of a curve in a river, on the down
drift side of the littoral drift beach zone or on deltas off of river mouths.
Samples are therefore, generally collected in these areas rather than mid-channel.
Sounding charts are extremely helpful for sample site selection since they show
the areas requiring the most dredging and, therefore, where the shoal material
is depositing. On a straight channel, lacking sounding information, a good
approach is to select sites on alternating sides of the channel.
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Areas likely to show the pollutional effects of man's activity should be
sampled. Therefore, where applicable, sample sites should be located in the
vicinity of marinas, loading docks, industrial or municipal outfalls, etc.
Due to laboratory resource constraints not all primary sites could be analyzed.
Based upon field evaluations of the quality of sediments, benthos, and potential
sources, those sites which appeared to be the "worst" were selected for
analysis. Samples from the remaining sites were logged, preserved, and
stored for future analysis should additional data be required.
Sampling Equipment
Grab samples were retrieved using a Ponar dredge. Core samples were taken
using a Wildco brass core tube 20" long with a 2" inner diameter and clear
Lexan plastic liner tube. The sediments were preserved by refrigeration
at 4°C. Multiple goals or core samples had to be composited at some sites
to obtain sufficient samples volunes. Duplicate samples were obtained on
at least ten percent of the sample sites.
Analytical Methodology
Prior to non-volatile organic analysis, the sediment samples were allowed to
thaw to 15-2b°C. Each sample was manually mixed and allowed to air dry. All
samples were ground with a mortar and pestle. Any sample requiring further
homogenization (discretion of analyst) was then passed through a 20 mesh
polypropylene sieve. The percent solids of the sample was determined on a
separate aliquot dried at 103-105°C.
-------
The presence of a broad range of volatile and non-volatile organic contaminants
was determined by GC/MS scans. The non-volative organics were removed from
the sediments by Soxhlet extraction with a 1:1 mixture of acetone and hexane.
A portion of the extract was passed through florisil and silica gel columns
for PCB and pesticide separation and analyzed by GC/tC. The organic extracts
were then injected into a Hewlett-Packard 5985 Gas Chromotograph/Mass Spectro-
meter. Volatile organic analysis was done on wet sediment diluted with organic-
free water. Concentration is later corrected for percent solids and reported
on a dry weight basis. The sediment and dilution water was purged with helium
and the volative organics were trapped on Tenax. The trap was desorbed onto
the GC column of a Hewlett-Packard 5985 GC/MS. All GC/MS scans and specific
GC analyses followed USEPA standard procedures for dealing with priority
pollutants. (Methods 608, 624, 625 Federal Register December 3, 1979).
Quantification of PCBs and pesticides was determined by subjecting the
sediment extracts to gas chromatography with electron capture detector
(GC/EC). Samples were air dried and sieved. Organic components were
removed from 20 grams of sample using Soxhlet extraction of 16 hours with
a solvent consisting of a 1:1 acetone/hexane (V:V) mixture. The extract
was concentrated and partitioned through florisil for the elimination of
interferences and separation of various pesticide mixtures. Further separation
of PCBs from pesticide components was done with silica gel. Quantitative
determination and confirmation was done using dual-column GC/EC on the ex-
tracts. The GC/EC extracts were also analyzed by GC/MS for additional
confirmation.
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Heavy metals were determined by first digesting the sediment samples in a
mixture of concentrated nitric and sulfuric acids. The acid extracts were
analyzed for arsenic, mercury, and selenium using standard USEPA flameless
absorption spectrometry. In addition, a scan for over 20 metals was made
using Inductively Coupled Argon Plasma (ICAP) techniques. All metals and
organic contaminants were reported as milligrams per kilograms (ppm) dry weight,
The following seven determinations of conventional pollutants were 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 sul fate-sulfuric acid and
mercuric oxide and refluxed for 2 hours. The COD of the sample is proportional
to the amount of dichromate chemically reduced during the procedure. Values
are reported as mg/kg COD.
Cyanide. Cyanide is converted to HCN by means of a reflux-distillation cata-
lyzed by copper chloride which decomposes metallic cyanide complexes. Cyanide
is determined spectrophotometrically as the cyanide is absorbed in a 0.2 N
NaOH solution. Cyanide concentrations are reported as mg CN-/kg dry sediment.
-6-
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Phenol. Manual distillation of phenolic compounds was used to remove inter-
ferences. The distillate reacts with buffered ferri-cyanide and 4 aminoanti-
pyrine spectrophotometrically at 505 nm. Phenol concentrations in the sediment
are reported as mg/kg dry sediment.
Phosphorus (total). Phosphorus was determined using a Technicon II Auto
Analyzer after block digestion of the sample. A 0.5g dry weight sample was
suspended in an HgO-04-H2S04 solution and digested at 200°C for 1 hour and
at 370°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 are calculated as:
%Solids = dry weight g x (100%)
wet wei ght 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-H^S04
sediment digest analyzed for total phosphorus. Nitrogen was quantified
as ammonia using the alkaline phenol-hypochlorite procedure.
-7-
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Quality assurance procedures set variance limits for reference samples, sample
splits, and spike samples. Any results obtained outside USEPA acceptance
limits were flagged as out-of-control and the samples rerun, if possible.
More detailed descriptions of the methodology for sediment analysis can
be obtained from USEPA, Region V, Central Regional Laboratory, 536 S. Clark
Street, Chicago, Illinois 60605.
-8-
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Results
Ashland, Wisconsin
Sediment samples were collected at five locations in the neashore waters of Che-
quamegon Bay off of Ashland, Wisconsin on May 21-22, 1981. (See Figure 1 and
Table 1). Samples from three of the sites, were analyzed (ASH 81-01, 03, and 05).
The Field Observations (Table 1) indicate sediments in the area sampled were
mostly sand with a thin layer of silt at some sites. Large wood chunks were
present in the sample from near the sewage treatment plant discharge (ASH
81-03) and the sediment sample from this site had an H2S odor, probably
indicating anoxic conditions. El odea, a rooted macrophyte (aquatic plant),
commonly called "waterweed," covered the bottom near the power plant outfall
(site ASH 81-01 and 02).
The conventional pollutants and metals analyses of the samples (Table 2) showed
high* levels of nutrients and metals in the sample near the power plant discharge
(ASH81-01). Sediments near the sewage treatment plant outfall (ASH 81-03) had
moderate levels of pollutants overall, except for a high total phosphorus,
mercury, copper, lead, and zinc concentrations. Pollutant levels in the sample
at the mouth of a small creek (ASH 81-05) were low.
PCBs and pesticides levels (Table 3) were at trace to low concentrations in all
samples. Among the samples analyzed at Ashland in this survey, the sample from
site ASH81-03 had the highest overall levels of PCBs and pesticides.
Table 4 lists the organic compounds sought in the samples with the GC/MS method
and their maximum detection limits. Table 5 shows the organic compounds identified
in the sediment samples with the GC/MS method. Pollutants identified were mostly
polynuclear aromatic hydrocarbons (PAHs).
*The terms low, moderate, high used in this report are derived by comparison
of the observed sediment concentrations to the USEPA Guidelines for the
Pollutional Classification of Great Lakes Harbor Sediments, (Appendix A)
for the parameters covered by the guidelines. For the parameters for which
guidelines have not been published, the terms are defined by comparing the
concentrations qualitatively to concentrations observed by the authors in
other Great Lakes harbor and river sediments.
-9-
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The sample from site ASH81-03 had elevated levels of PAHs. Samples from the
other sites had trace to low concentrations. Trace to low levels of some
volatile organics were also identified in the sample from ASH81-03.
Table 6 contains the data for organic compounds that were tentatively
identified by GC/MS. This means the compounds had a high similarity ratio
to the library mass spectra of the listed compounds, but were not confirmed
or accurately quantified by running the sample against actual standards of
the tentatively identified compound. The sample from ASH81-03 had the
greatest variety of compounds tentatively identified.
Conclusions
Sediments near the discharge of the sewage treatment plant (ASH81-03) were
contaminated with phosphorus mercury and PAHs. From the physical characteristics
of the surroundings (i.e., water depth, cobble and coarse sand around the
sample sites, the thin layer of organic material) it appears that the contaminated
sediments may be of fairly recent origin at this site. The sewage treat-
ment plant discharge would seem the most likely source of the contamination
although coal dust or spillage from coal handling facilities in the area could
also be responsibile for the elevated PAH levels.
Sediments near the power plant (ASH81-01) were high in nutrients and metals
and had traces of PAHs. The presence of el odea ("waterweed") near the power
plant (sites ASH81-01 and 02) probably indicates a low-energy environment,
because el odea prefer such an environment. Thus, the contamination may be of
more historical origin. Also, the high organic level (total volatile solids
of 26.3%) may be largely responsible for the high levels of the other metals,
because pollutants tend to adsorb to organic matter.
-10-
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1000 0 1000 ..'000 )000 4000 WOO 6000 7000 FLU
1 b 0 1 CILOMCTFR „ t^
ll
H v>
Lake P
ASHLAND. WISCONSIN
Sediment Sampling Sites
May 21-22, 1981
Great Lakes National Program Office
USEPA Chicago. IL.
* Sample! Atulyiod
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Table 1
Field Observations:
Ashland, Wisconsin, May 21-22, 1981
Sample Site Sample Site and Sediment Description
ASH 81-01 30' offshore from power plant outfall in
5' of water, bottom was fine silt, sand
with el odea covering bottom. No corer pene-
tration (2" maximum).
ASH 81-02 75' offshore from plant outfall in 7' of
water. Bottom was silt and sand with
detritus and el odea.
ASH 81-03 15' offshore in 8' of water, near the sewage
treatment plant. Large wood chunks were
present. Sludge was present. There was
an H2$ odor in the sludge. No corer pene-
tration (2" maximum). Coarse sand and
cobble outside of immediate area.
ASH 81-04 10' from shore in 3-4' of water. Bottom
was all sand and cobble in the area.
Sample was taken about 30' east of debris
pilings.
ASH 81-05 5' offshore, at the mouth of a creek (little
flow) in 3' of water. Bottom was all sand
in the area, no organic deposits were found.
-12-
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Table 2
Sediment Concentrations of Some Conventional Pollutants and Metals:
Ashland, Wisconsin, May 21-22, 1981
(All values are mg/kg dry weight unless otherwise noted)
Location Sample Site Number
Parameter
Total Solids (%)
Volatile Solids (%)
Total Kjeldahl Nitrogen
Total Phosphorus
COD mg/g
Mercury
Silver
Boron
Barium
Beryllium
Cadmium
Cobalt
Chromium
Copper
Lithium
Manganese
Molybdenum
Nickel
Lead
Tin
Strontium
Vanadium
Yttrium
Zinc
Calcium (mg/g
Potassium (mg/g
Maynesuim (mg/g
Sodium (mg/g
Aluminum (mg/g
Iron (rng/g)
ASH 81
-01
39.3
26.3
L 2100
480
29.
0.3
6.7
W8.0
240
WO.l
6.3
14.0
130
160
37
490
1.7
92
410
15
64
32
12
600
42
2.2
13.0
0.3
17
30
ASH 81
-03
62.3
7.6
1300
2100
55
2.4
14
W8.0
390
WO.l
1.0
3.4
18
170
3.7
95
Wl.O
6.6
380
20
26
11
4.1
320
4.7
0.3
2.2
0.1
3.6
6.3
ASH 81
-05
71.8
1.0
96
220
2.4
U.I
0.3
W8.0
18
WU.l
L WO. 2
WO. 6
L 3.0
0.9
Wl.O
150
Wl.O
L 4.9
W7.0
W4.0
11
3.1
1.5
25
1.5
0.1
1.5
WO.l
2.2
7.2
Reporting Codes:
A "W" notation means the concentration was below the stated level, which was
the minimum instrument response level.
A "K" notation means the chemical was present but below the stated concentration,
which is the normal limit of quantification.
A "T" notation means the chemical was present above the method detection
limit but below the limit of quantification.
A "ND" notation means there was no instrument response at all.
-13-
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Table 3
Sediment Concentrations of PCBs and Pesticides by the GC/EC Method:
Ashland, Wisconsin, May 21-22, 1981
(All values are mg/kg dry weight unless otherwise noted)
Location Sample Site Number
Parameter
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
o,p-DDE
p.p'-DDE
o,p-DDD
p.p'-DDD
o,p-DDT
p,p'-DDT
g-Chlordane
OxyChlordane
Hepjtachlor epoxide
Zytron
b-BHC
g-BHC
Hexachlorobenzene
Trifluralin
Aldrin
Heptachlor
Methoxychlor
Endrin
DCPA
Endosulfan I
Endosulfan II
Dieldrin
Di-n-butyl phthalate
ASH 81
-01
.021
.029
.019
.014
.015
.007
ND
ND
.007
<.001
ND
.001
ND
.010
.003
.002
<.001
ND
ND
ND
.002
.001
.005
ND
.004
.002
.308
ASH 81
-01DUP
.022
.030
.019
.010
.003
.004
ND
ND
.009
.015
<.001
<.001
ND
.014
.003
.002
ND
ND
<.001
ND
ND
.001
.004
ND
.004
.001
.313
ASH 81
-03
.021
.060
.017
.105
ND
.007
<.001
.008
.012
.003
.005
.001
ND
.009
ND
ND
.002
.016
.005
ND
.006
ND
ND
ND
.006
ND
.373
ASH 81
-05
.039
.082
ND
ND
ND
ND
ND
ND
ND
.002
<.001
<.001
ND
.004
ND
ND
.005
.009
<.001
ND
ND
ND
ND
ND
.003
ND
.148
Reporting Codes:
A "W" notation means the concentration was below the stated level, which was
the minimum instrument response level.
A "K" notation means the chemical was present but below the stated concentration,
which is the normal limit of quantification.
A "T" notation means the chemical was present above the method detection
limit but below the limit of quantification.
A "ND" notation means there was no instrument response at all.
-14-
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Table 4
Organic Compounds Sought in Sediments by the GC/MS Method and Maximum Detection
Limits:
Ashland, Wisconsin, May 21-22, 1981
(Actual detection limits for individual samples may vary as a function of in-
teferences present, aliquot size, degree of pre-concentration, etc.)
(All values are mg/kg dry weight unless otherwise noted)
Semi Volatiles
Compound B/N/A Mixtures Maximum Detection limit (mg/kg)
Hexachloroethane 3.1
Hexachlorobutadiene 2.26
Chlorinated Aromatics
1,2-Dichlorobenzene 1.3
1,3-Dichlorobenzene 1.1
1,4-Dichlorobenzene 1.0
1,2,4-Trichlorobenzene 1.7
Hexachlorobenzene 1.34
2-Chloronaphthalene 0.96
Chlorinated Phenolics
2-Chlorophenol 1.7
2,4-Uichlorophenol 2.52
2,4,6-Trichlorophenol 4.22
Pentachlorophenol 6.72
p-Chloro-m-cresol 1.8
Halogenated Ethers
bis (2-Chloroethyl) ether 1.4
4-Bromophenylphenyl ether 2.38
bis(2-Chloroethoxy) methane 1.0
Phenolics
Phenol 5.34
2,4-Dimethylphenol 0.52
p-t-Butylphenol 1.3
Nitro Aromatics
Nitrobenzene 7.26
2-Nitrophenol 4.22
4-Nitrophenol 19.1
4,6-Dinitro-o-cresol 11.0
2,4-Dinitrotoluene 4.66
2,6-Dinitrotoluene 2.94
-15-
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Polynuclear Aromatic Hydrocarbons
Naphthalene
Acenaphthene 1.2
Acenaphthylene 0.28
Fluorene 1.0
Anthracene/Phenanthrene 0.18
Fluoranthene 0.56
Pyrene 0.55
Chrysene/Benz(a)anthracene 1.7
Benzo(b)fluoranthene 2.0
Benzo(a)pyrene 3.66
Indeno(l,2,3-cd)pyrene 1.3
Perylene 2.66
Benzo(g,h,i)perylene 11.3
Phthalate Esters
Dimethyl phthalate 1.0
Diethyl phthalate 2.0
Di-n-butyl phthalate
Di-n-octyl phthalate 1.48
Butyl benzyl phthalate 4.08
bis(2-Ethylhexyl) phthalate
Nitrosamines
N-Nitrosodipropylamine 1.6
N-Nitrosodiphenyl amine 1.5
Miscellaneous
Isophorone 4.08
1,2-Diphenylhydrazine 1.00
Dibromobiphenyl 1.7
-16-
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Volatile Urganics Analysis
Halomethanaes
Uichloromethane .0027
Tricnloromethane .0035
Tetrachloromethane .0043
Tribromomethane .0025
Dibromochloromethane .0015
Bromodichloromethane .001
Trichlorofluoromethane .0105
Chlorinated Ethanes
1,1-Uichloroethane .0034
1,2-Dichloroethane .0025
1,1,1-Trichloroethane .0027
1,1,2-Trichloroethane .0042
1,1,2,2-Tetracnloroethane .0037
Chlorinated Ethylenes
1,1-Dichloroethylene .0098
1,2-Dichloroethylerie .0036
Trichloroethylene .0021
Tetrachloroethylene .0026
Chlorinated Propanes and Propenes
1,2-Dichloropropane .0051
cis-l,3-0ichloro-l-propene .0025
trans-l,3-Dicnloro-1-propene .0020
Aromatics
Benzene .0008
Methyl benzene .0008
Ethyl benzene .0008
1,3-Dirnethylbenzene .0006
1,2 - and 1,4-Dimethylbenzene .0006
Chlorobenzene .0009
-17-
-------
PCBS
1. Monochlorobiphenyl 2.94
2. Dichlorobiphenyl (1) 3.12
3. Dichlorobiphenyl (2) 2.10
4. Trichlorobiphenyl (1) 2.54
5. Trichlorobiphenyl (2) 2.18
6. Trichlorobiphenyl (3) 1.22
7. Trichlorobiphenyl (4) 1.9
8. Tetrachlorobiphenyl (1) 3.10
9. Tetrachlorobiphenyl (2) 1.9
10. Tetrachlorobiphenyl (3) 2.52
11. Tetrachlorobiphenyl (4) 2.40
12. Tetrachlorobiphenyl (5) 2.48
13. Tetrachlorobiphenyl (6) 1.6
14. Tetrachlorobiphenyl (7) 1.5
15. Pentachlorobiphenyl (1) 1.8
16. Pentachlorobiphenyl (2) 1.7
17. Pentachlorobiphenyl (3) 2.44
18. Pentachlorobiphenyl (4) 2.34
19. Pentachlorobiphenyl (5) 2.0
20. Pentachlorobiphenyl (6) 2.0
21. Hexachlorobiphenyl (1) 1.8
22. Hexachl orobiphenyl (2) 1.6
23. Hexachlorobiphenyl (3) 2.0
24. Hexachl orobiphenyl (4) 2.1
25. Heptachlorobiphenyl (1) 4.54
26. Heptachl orobiphenyl (2) 2.68
27. Heptachlorobiphenyl (3) 2.10
28. Heptachlorobiphenyl (4) 2.92
29. Heptachlorobiphenyl (5) 2.02
Pesticidies
1. Triflan(Trifluralin) 1.9
2. g-BHC 4.90
3. Hexachlorobenzene 1.3
4. 2,4-D, Isopropyl Ester 6.98
5. b-BHC 12.5
6. a-BHC 16.5
7. Heptachl or 6.04
8. Di-n-Butyl phthalate
9. Zytron 2.72
10. Aldrin 5.94
11. DCPA 1.6
12. Isodrin 6.72
13. Heptachlor epoxide 4.48
14. Oxychlordane 20.2
15. g-Chlordane 3.56
16. o,p DDE 1.8
17. Endosulfan I 25.92
18. p.p'-DDE 2.52
19. Dieldrin 14.0
20. o,p-DDD 1.7
21. Endrin 6.60
22. Chlorobenzilate 3.36
23. Endosulfan II 40.30
24. o.p-DDT & p,p'-DDD 2.38
25. Kepone(Chlordecone) 5.42
26. p,p'-DDT 3.82
27. Methoxychlor 3.90
28. Tetradifon 7.88
29. Mi rex -i«- 3.12
-------
Table 5
Organic Compounds Identified in Sediments by the GC/MS Method:
Ashland, Wisconsin, May 21-22, 1982
(All values are mg/kg dry weight unless otherwise noted)
Location Sample Site Number
Parameters
ASH 81
01
ASH 81
01DUP
Semi Volatile Organ ics
B/N/A Mixtures
Polynuclear Aromatic Hydrocarbons
Acenaphthene
Acenaphthylene
Naphthalene
Anthracene/Phenanthrene
Fl uorene
Fluoranthene
Chrysene/Benz(a)anthracene
Benzo(b)fluoranthene
Pyrene
Benzo(a)pyrene
Perylene
Benzo(g,h,i )perylene
Indeno(l,2,3-cd)pyrene
Phthalate Esters
Di-n-butyl phthalate
bis(2-Ethylhexyl) phthalate
Halomethanes
Dichl oromethane
Dibromochl oromethane
Tribromomethane
Aromatics
Benzene
Methyl benzene
1.77
6.28
1.1
2.72
2.58
1.14
6.06
0.171
1.72
5.2
1.05
2.36
2.4
1.72
3.55
0.017
0.012
ASH 81
03
2.44
0.42
2.16
6.16
1.67
15.62
25.0
12.6
15.18
1.83
5.03
1.22
44.5
4.05
0.006
0.009
0.018
0.009
ASH 81
05
0.64
4.94
0.66
1.79
-19-
-------
Table 6
Organic Compounds Tentatively Identified in Sediments by the 6C/MS Method:
Ashland, Wisconsin, May 21-22, 1981
(i.e., compounds with high similarity to library mass spectra of the compound,
but not run against actual standards of the compound)
Location Sample Site Number
Parameter
Polynuclear Aromatic Hydrocarbons
and Derivatives
Benzo(g,h,i )fl uoranthene
Methyl naphthalene
Dimethyl naphthal ene
Trimethyl naphthal ene
Methyl phenanthrene
Dimethyl phenanthrene
Methyl i sopropyl phenanthrene
Methyl pyrene
Methyl benz(a)anthracene
Methyl fl uoranthene
Dibenzothiophene
Aromatics and Derivatives
Ethyl toluene (1)
Ethyl toluene (2)
Cymene
Propyl toluene
Phenols and Cresols
Cresol
Miscellaneous
Palmitic acid
Stearic acid
Cholestan-3-ol
Pinene
Methyl i sopropyl cycl ohexane
Hydrocarbons
VOLATILE!
Di ethyl ether
Deuterochl oroform
ASH 81
01
*
*
*
*
*
*
*
*
*
ASH 81
03
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
ASH 81
05
*
*
*
*Compound tentatively identified in sample from this site.
-20-
-------
Black River, Michigan
Sediment samples were collected at five locations near the outlet of the
Black River to Lake Superior (Figure 2 and Table 7). The sample from the
middle of the harbor area (BRH81-03) was analyzed.
The Field Observations (Table 7) show silt and detritus at most of the sites
sampled. No oil was observed in the samples, nor were odors observed. Some
scuds (macrobenthos) were observed in the samples from the center of the harbor
(BRH81-03 and 05).
The analyses for conventional pollutants and metals (Table 8) show low levels
for all pollutants except phosphorus and manganese, which exhibited moderate
levels.
The pesticides and PCB analyses (Table 9) show trace leves of PCBs and a few
pesticides.
Table 10 lists the organic compounds sought in the samples with the GC/MS
method and their maximum detection limits. Table 11 shows the compounds
that were identified in the sample by the GC/MS method. Traces of benzenes
were found in the sample.
Table 12 lists the organic compounds that were tentatively identified by the
GC/MS method. Only hydrocarbons and a trace of diethyl ether were tentatively
identified.
Conclusions
Sediments near the outlet of the Black River, Michigan to Lake Superior had
low levels of organic and inorganic pollutants.
-21-
-------
Figure 2.
BLACK RIVER, MICHIGAN
Sediment Sampling Sites
May 22, 1981
Great Lakes National Program Office
USEPA Chicago, IL.
* S»mpl»» Anilyltd
100 0
9 1000
LAKE SUPERIOR
-------
Table 7
Field Observations:
Black River, Michigan, May 22, 1981
Sample Site Sample Site and Sediment Description
BRH 81 -
01 50' downstream from pedestrian bridge at
park on east bank of river along shoal, in
10' of water. Sediments were fine sand,
silt, detritus, no organisms observed in
3 casts. Other upstream main channel sites
with coarse gravel and rocks, not amenable
to sampling. No odor, oil, color of sand
sand and detritus.
02 Along west breakwall in 1' of water. Deeper
water had too much cobble to sample. Only
1 grab at this area produced the chemistry
sample. No odor, oils, sample was clay arid
sand.
03 At center of harbor area, fine silts and
detritus present. Some scuds present.
Sample collected in 10' of water. No odors,
oil, color of red clay and detritus.
04 Along east breakwall in 3' of water.
Sediments were fine silt. No odor or
oil observed.
05 Middle of entrance to harbor in 17' of
water. Some silt and detritrus. A few
scuds observed. No odor or oil.
-23-
-------
Table 8
Sediment Concentrations of Some Conventional Pollutants and Metals:
Black River, Michigan, May 22, 1981
(All values are mg/kg dry weight unless otherwise noted)
Location Sample Site Number
Parameter
Total Solids (%)
Volatile Solids (%
)
Total Kjeldahl Nitrogen
Total Phosphorus
COD (mg/g)
Mercury
Silver
Boron
Barium
Beryll ium
Cadmium
Cobalt
Chromium
Copper
Lithium
Manganese
Molybdenium
Nickel
Lead
Tin
Strontium
Vanadium
Yttrium
Zinc
Calcium (mg/g
Potassium (mg/g
Magnesium mg/g
Sodium 'tmg/g
Aluminum (mg/g
Iron (mg/g
BRH 81
03
61.7
2.91
650
470
25
0.1
.3W
8W
43
0.1W
0.2W
9.2
10
13
8.5
320
LOW
14
9.4
4.0W
14
31
10
40
5.1
0.3
4.6
0.1
7.5
8.3
Reporting Codes:
A "W" notation means the concentration was below the stated level, which
was the minimum instrument response level.
A "K" notation means the chemical was present but below the stated con-
centration, which is the normal limit of quantification.
A "T" notation means the chemical was present above the method detection
limit but below the limit of quantification.
A "ND" notation means there was no instrument response at all.
a=alpha; b=beta; d=delta; g=ganna
-24-
-------
Table 9
Sediment Concentrations of PCBs and Pesticides by the 6C/EC Method:
Black River, Michigan, May 22, 1981
(All values are mg/kg dry weight unless otherwise noted)
Location Sample Site Number
Parameters
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
o.p-UDE
p.p-DDE
o.p-DDD
p.p-UDD
o,p-UOT
p.p-UDT
g-Chlordane
Oxy-Chlorddne
Heptaclor epoxide
Zytron
b-BHC
g-BHC
Hexachlorobenzene
Trifluralin
Aldrin
Heptaclor
Methoxychlor
Endrin
DC PA
Endosulfan I
Endosulfan II
Dieldrin
Di-n-butyl phthalate
BRH 81
03
.015
.036
.006
ND
NO
.001W
ND
ND
ND
.002
.002
.002
ND
.006
ND
ND
.002
.005
.001W
ND
ND
ND
ND
ND
.002
ND
.104
BRH 81
03DUP
.014
.033
.005
ND
ND
.001W
ND
ND
ND
.002
.002
NU
ND
.007
ND
ND
.003
.004
ND
ND
ND
ND
.001W
ND
.002
ND
.119
Reporting Codes:
A "W" notation means the concentration was below the stated level, which
was the minimum instrument response level.
A "K" notation means the chemical was present but below the stated con-
centration, which is the normal limit of quantification.
A "T" notation means the chemical was present above the method detection
limit but below the limit of quantification.
A "ND" notation means there was no instrument response at all.
a=alpha; b=beta; d=delta; g=ganna
-25-
-------
Table 10
Organic Compounds Sought in Sediments by the GC/MS Method and Maximum Detection
Limits:
Black River, Michigan, May 22, 1981
(Actual detection limits for individual samples may vary as a function of
interferences present, aliquot size, degree of pre-concentration, etc)
(All values are mg/kg dry weight unless otherwise noted)
Chlorinated Aliphatics
Hexachloroethane .29
Hexachlorobutadiene .21
Chlorinated Aromatics
1,2-Dichlorobenzene .12
1,3-Dichlorobenzene .11
1,4-Dichlorobenzene .10
1,2,4-Trichlorobenzene .17
Hexachlorobenzene .26
2-Chloronaphthalene .11
Chlorinated Phenolics
2-Chlorophenol .17
2,4-Dichlorophenol .24
2,4,6-Trichlorophenol .37
Pentachlorophenol .74
p-chloro-m-cresol .17
Halogenated Ethers
bis(2-Chloroethyl) ether .12
4-Bromophenlyphenyl ether .40
bis(2-Chloroethoxy)methane .08
Phenolics
Phenol 2.19
2,4-Dimethylphenol .13
p-t-butylphenol .14
Nitro Aromatics
Nitrobenzene 1.80
2-Nitrophenol .31
4-Nitrophenol 2.81
4,6-Dinitro-o-cresol 3.91
2,4-Dinitrotoluene .57
2,6-Dinitrotoluene .34
-26-
-------
Polynuclear Aromatic Hydrocarbons
Naphthalene .05
Acenaphthene .12
Acenaphthylene .07
Fluorene .13
Anthracene/Phenanthrene .09
Fluoranthene .13
Pyrene .14
Chrysene/Benz(a)anthracene .22
Benzo(b)Fluoranthene .09
Benzo(a)pyrene .09
Indeno(l,2,3-cd)pyrene .09
Perylene .09
Benzo(g,h,i)perylene .09
Phthalate Esters
Dimethyl phthalate .12
Diethyl phthalate 1.34
Di-n-butyl phthalate
Di-n-octyl phthalate .37
Butyl benzyl phthalate .35
bis(2-Ethylhexyl) phthalate .28
Nitrosamines
N-Nitrosodipropyl amine .10
N-Nitrosodiphenylamine .16
Miscellaneous
Isophorone .10
1,2-Diphenylhydrazine .08
Dibromobiphenyl .33
-27-
-------
Volatile Organics Analysis
Halomethanes
Dichloromethane
Trichloromethane .0016
Tetrachloromethane .0012
Tribromomethane .0029
Dibromochloromethane .002
Bromodichloromethane .0016
Trichlorof1uoromethane ' .0012
Chlorinated Ethanes
1,1-Dichloroethane .0044
1,2-Uichloroethane .0045
1,1,1-Trichloroethane .0012
1,1,2-Trichloroethane .007
1,1,2,2-Tetrachloroethane .0042
Chlorinated Ethylenes
1,1-Dichloroetnylene .0032
1,2-Dichloroethylene .0027
Trichloroethylene .0022
Tetrachloroethylene .0018
Chlorinated Propanes and Propenes
1,2-Dichloropropane .0067
cis-1,3-Uichloro-1-propene .0057
trans-1,3-Dichloro-1-propene .0037
Aromatics
Benzene
Methyl benzene
Ethyl benzene .0006
1,3-Dimethyl benzene .0008
1,2- and 1,4-Dimethyl benzene .0009
Chlorobenzene .0011
-28-
-------
PCBs
1. Monochlorobiphenyl .73
2. Dichlorobiphenyl (1) .69
3. Dichlorobiphenyl (2) .60
4. Trichlorobiphenyl (1) .79
5. Trichlorobiphenyl (2) .67
6. Trichlorobiphenyl(3) 1.17
7. Trichlorobiphenyl(4) .41
8. Tetrachlorobiphenyl(1) 1.32
9. Tetrachlorobiphenyl (2) .04
10. Tetrachlorobiphenyl(3) .74
11. Tetrachlorobiphenyl(4) 1.00
12. Tetrachlorobiphenyl(5) .62
13. Tetrachlorobiphenyl (6) 1.11
14. Tetrachlorobiphenyl(7) .87
15. Pentachlorobiphenyl(1) .57
16. Pentachlorobiphenyl(2) 1.30
17. Pentachlorobiphenyl(3) .74
18. Pentachlorobiphenyl(4) .73
19. Pentachlorobiphenyl(5) .97
20. Pentachlorobiphenyl(6) .80
21. Hexachlorobiphenyl (1) 1.43
22. Hexachlorobiphenyl (2) .48
23. Hexachlorobiphenyl (3) .49
24. Hexachlorobiphenyl (4) .19
25. Heptachlorobiphenyl(1) 1.12
26. Heptachlorobiphenyl(2) .67
27. Heptachlorobiphenyl(3) .52
28. Heptachlorobiphenyl(4) .73
29. Heptachlorobiphenyl(5) 1.76
Pesticides
1. Triflan(Triflural in) .47
2. g-BHC 1.22
3. Hexachlorobenzene .26
4. 2,4-D, Isopropyl ester 1.73
5. b-BHC 10.0
6. a-BHC 1.05
7. Heptachlor 1.50
8. Di-n-Butyl phthalate
9. Zytron .68
10. Aldrin 1.48
11. DCPA .40
12. Isodrin 1.67
13. Heptachlor epoxide 1.11
14. Oxychlordane 5.00
15. g-chlordane .88
16. o.p-DDE .45
17. Endosulfan I 6.43
18. p,p'-DDE .62
19. Dieldrin 3.46
20. o.p-DDD .43
21. Endrin 1.64
22. Chlorobenzilate .83
23. Endosulfan II 10.0
24. o,p-DDT & p,p'-DDD .59
25. Kepone (Chordecone) 1.34
26. p,p'-DDT .95
27. Methoxychlor .97
28. Tetradifon 2.90
29. Mi rex -?Q- .78
-------
Table 11
Organic Compounds Identified in Sediments by the GC/MS Method:
Black River, Michigan, May 22, 1981
(All values are mg/kg dry weight unless otherwise noted)
Location Sample Site Number
Parameter
Benzene
Methyl benzene
Semi
Base Nc
Di-n-butyl phthalate
BRH 81
03
Volatil
.031
.007
Volatile
jutral Ac
0.54
e Organics
; Organics
:id Mixtures
-30-
-------
Table 12
Organic Compounds Tentatively Identified in Sediments by the GC/MS Method:
Black River, Michigan, May 22, 1981
(i.e., compounds with high similarity to library mass spectra of the
compound, but not run against actual standards of the compound)
Location Sample Site Number
Parameter
Hydrocarbons
Di ethyl ether
BRH 81
03
Semi -Vole
*
Volatile (
*
itile Organics
)rganics
*Compound tentatively identified in sample from this site.
-31-
-------
L'Anse, Michigan
Sediment samples were collected at 8 sites near L'Anse, Michigan in the near-
shore of Lake Superior and the Falls River (Figure 3 and Table 13). Three of
the samples (LAN81-03,04,and 07) were analyzed.
The field observations (Table 13) show sediments were sand or sand with some
silt. Some sludge-like material was found at site LAN81-03, near the sewage
treatment plant submerged outfall. Some macrophytes (aquatic plants) were
found at this site.
The analyses for conventional pollutants and metals (Table 14) generally show low
levels of pollutants in all samples. The sample from site LAN81-07 at the mouth
of the Falls River had moderate levels of total kjeldahl nitrogen, CUD, and copper.
The PCBs and pesticides analyses (Table Ib) show traces of PCBs and some pesticides
in the samples. Of the samples analyzed in this survey at L'Anse, the sample
from LAN81-07 had the greatest variety of pesticides identified, albeit at
trace levels.
Table 16 lists the organic compounds sought in the sediment samples by the GC/MS
method and their detection limits. Table 17 shows the compounds that were identi-
fied by the GC/MS analysis. Traces of PAHs were found in the sample from LAN81-
04. Traces of some benzene compounds were identified in the samples.
Table 18 shows the organic compounds that were tentatively identified in the
samples by the GC/MS method.
Summary
Sediments sampled at L'Anse had low levels of organic and inorganic pollutants.
-32-
-------
LAKE SUPERIOR
L'ANSE, MICHIGAN
Sediment Sampling Sites
May 23,1981
Great Lakes National Program Office
USEPA Chicago, IL.
-------
Table 13
Field Observations:
L'Anse, Michigan, May 23, 1981
Sample Site Sample Site and Sediment Description
LAN 81-
01 On Southwest side of harbor, in Fall River
Channel, 200' upstream from outer corner of
Celotex Corp dock in 4' of water. Sandy bottom
with some silt, below all Celotex Corp. outfalls.
02 Within harbor on Northeast side, 2b' from boat
ramp, 20' from storm sewer outfall, 15' south-
west of docking area in 3' of water. Whole area
is sandy. Sample was sand witn little silt.
03 In area of submerged sewer outfall in 11' of
water. Sand and silt with some sludge-like
organic matter. Macrophyte growing shoots
present. 400' offshore (submerged sewer out-
fall was not actually found).
04 In area of sewer pipes near STP pump house, 15'
offshore in 3' of water. Sand and silt present.
No evidence of sewage outfall.
05 500' from shore, near the end of a submerged sewer
pipe in 20' of water. Coarse sand and silt. A
trace of organic matter present.
06 Middle of sand spit, northeast shore at sewer
outfall, in area where all shoreline outfalls
should be carried by currents. Sampled in 3' of
water, 10' offshore.
07 Along southwest bank of Fall River, (undercut
channel following bank with pools 4 to 10' deep)
in pool 4' deep. Sample taken from shore by hand
cast. Sediments were silt and sand with some
organic matter. Site was approximately even
with the mouth of the Fall River at L'Anse Harbor.
08 Immediately below bridge on Fall River at Celotex
plant entrance, on Northeast side of River. Sample
taken from shore by hand cast in 2' of water.
Sediments in the area were sand, silt-some organic
detritus, intermittent cobble. There were approx-
imately 8 outfall pipes between sites LAN81-07 and
08. Most parking lot storm water drain pipes, but
3 were submerged outfalls. No discharge was apparent
from any of these pipes.
-34-
-------
Table 14
Sediment Concentrations of Some Conventional Pollutants and Metals:
L'Anse, Michigan, May 23, 1981
(All values are mg/kg dry weight unless otherwise noted)
Location Sample Site Number
Parameter
Total Solids (%)
Volatile Solids (%)
Total Kjeldahl Nitrogen
Total Phosphorus
COD (mg/g)
Mercury
Silver
Boron
Barium
Beryllium
Cadmium
Cobalt
Chromium
Copper
Lithium
Manganese
Molybdenium
Nickel
Lead
Tin
Strontium
Vanadium
Yttrium
Zinc
Calcium
Potassium
Magnesium
Sodium
Aluminum
Iron
mg/g
mg/g
mg/g
mg/g
mg/g
mg/g
LAN 81
03
66.8
0.86
230
380
5.9
0.1
.3W
8W
12
. 1W
.2W
2.3
6
12
3.7
67
1W
6.1
10
4W
3.4
11
5.2
23
1.2
0.1W
1.7
0.1W
2.7
5.6
LAN 81
04
72.5
0.47
57
280
.38
0.1
.3W
8W
12
.1W
.2W
2.4
6
11
5.6
100
1W
8.0
8
4W
3.7
12
7.2
29
1.3
0.2
2.4
0.1W
3.5
6.7
LAN 81
07
56.1
4.33
1200
370
48.
0.1
.3W
8W
32
. 1W
.2W
3.2
10
28
6.6
200
1W
7.8
17
4w
6.5
13
6.1
42
2.3
L 0.2
2.2
0.1W
4.5
7.2
Reporting Codes:
A "W" notation means the concentration was below the stated level, which
was the minimum instrument response level.
A "K" notation means the chemical was present but below the stated con-
centration, which is the normal limit of quantification.
A "T" notation means the chemical was present above the method detection
limit but below the limit of quantification.
A "ND" notation means there was no instrument response at all.
-35-
-------
Table 15
Sediment Concentrations of PCBs and Pesticides by the GC/EC Method:
L'Anse, Michigan, May 23, 1981
(All values are mg/kg dry weight unless otherwise noted)
Location Sample Site Number
Parameters
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
o.p-DDE
p,p'-DDE
o.p-DDD
p,p'-DDD
o.p-DDT
p.p'-DT
g-Chlordane
Oxy-Chlordane
Heptaclor Epoxide
Zytron
b-BHC
g-BHC
Hexachl orobenzene
Trifluralin
Aldrin
Heptaclor
Methoxychlor
Endrin
DCPA
Endosul fan I
Endosulfan II
Dieldrin
Di-n-butyl phthalate
LAN 81
03
.008
.011
.009
.003
ND
ND
ND
ND
ND
.001
ND
ND
ND
ND
ND
ND
.001
ND
ND
ND
ND
ND
.001W
ND
.002
ND
.137
LAN 81
03-DUP
.007
.007
.004
ND
ND
ND
ND
ND
ND
.002
ND
ND
ND
ND
ND
ND
.001W
.003
ND
ND
ND
ND
ND
ND
.003
ND
.104
LAN 81
04
ND
ND
.004
ND
ND
.001W
.001W
ND
ND
.001W
ND
ND
ND
ND
ND
ND
.001W
ND
ND
ND
ND
ND
ND
ND
.004
ND
.123
LAN 81
07
.019
.047
.007
.005
ND
ND
ND
ND
ND
.002
.001W
ND
ND
ND
ND
ND
.003
.008
.001W
.003
ND
ND
.001W
ND
.002
ND
.119
Reporting Codes:
A "W" notation means the concentration was below the stated level, which
was the minimum instrument response level.
A "K" notation means the chemical was present but below the stated con-
centration, which is the normal limit of quantification.
A "T" notation means the chemical was present above the method detection
limit but below the limit of quantification.
A "ND" notation means there was no instrument response at all.
a=alpha; b=beta; d=delta; g=gamma
-36-
-------
Table 16
Organic Compounds Sought in Sediments by the GC/MS Method and Maximum Detection
Limits:
L'Anse, Michigan, May 23, 1981
(Actual detection limits for individual samples may vary as a function of
inteferences present, aliquot size, degree of pre-concentration, etc).
(All values are mg/kg dry weight unless otherwise noted)
Compound B/N/A Mixtures
Chlorinated Aliphatics
Hexachloroethane
Hexachlorobutadi ene
Chlorinated Aromatics
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2,4-TM chl orobenzene
Hexachlorobenzene
2-Chloronaphthalene
Chlorinated Phenolics
2-Chlorophenol
2,4-Dichlorophenol
2,4,6-Trichlorophenol
Pentachlorophenol
p-Chloro-m-cresol
Halogenated Ethers
bis(2-Chloroethyl) ether
4-Bromophenylphenyl ether
bis(2-Chloroethoxy)methane
Phenolics
Phenol
2,4-Dimethylphenol
p-t-butylphenol
Maximum Detection Limit (mg/kg)
.39
.28
.17
.15
.14
.22
.35
.15
.23
.33
.50
.99
.22
.16
.54
.11
2.94
.17
.18
-37-
-------
Nitro Aromatics
Nitrobenzene 2.41
2-Nitrophenol .41
4-Nitrophenol 3.77
4,6-Dinitro-o-cresol 5.24
2,4-Dinitrotoluene .77
2,6-Dinitrotoluene .46
Polynuclear Aromatic Hydrocarbons
Naphthalene .07
Acenaphthene .16
Acenaphthylene .10
Fluorene .17
Anthracene/Phenanthrene .12
Fluoranthene .15
Pyrene .16
Chrysene/Benz(a)anthracene .26
Benzo(b)fluoranthene .16
Benzo(a)pyrene .12
Indeno(l,2,3-cd)pyrene .12
Perylene .12
Benzo(g,h,i)perylene .12
Phthalate Esters
Dimethyl phthalate .16
Diethyl phthalate 1.80
Di-n-butyl phthalate
Di-n-octyl phthalate .49
Butyl benzyl phthalate .47
bis(2-Ethylhexyl) phthalate .33
Nitrosamines
N-Nitrosodipropyl amine .14
N-Nitrosodiphenylamine .22
Miscellaneous
Isophorone .14
1,2-Diphenylhydrazine .10
Dibromobiphenyl .44
-38-
-------
PCBs
1. Monochlorobiphenyl .98
2. Dichlorobiphenyl (1) .92
3. Dichlorobiphenyl (2) .80
4. Trichlorobiphenyl (1) 1.06
5. Trichlorobiphenyl (2) .89
6. Trichl orobiphenyl (3) 1.56
7. Trichlorobiphenyl (4) .55
8. Tetrachlorobiphenyl (1) 1.77
9. Tetrachlorobiphenyl (2) .05
10. Tetrachlorobiphenyl (3) .99
11. Tetrachl orobiphenyl (4) 1.34
12. Tetrachl orobiphenyl (5) .83
13. Tetrachl orobiphenyl (6) 1.49
14. Tetrachlorobiphenyl (7) 1.16
15. Pentachlorobiphenyl (1) .77
16. Pentachlorobiphenyl (2) 1.75
17. Pentachlorobiphenyl (3) .99
18. Pentachlorobiphenyl (4) .98
19. Pentachlorobiphenyl (5) 1.30
20. Pentachlorobiphenyl (6) 1.07
21. Hexachlorobiphenyl (1) 1.91
22. Hexachlorobiphenyl (2) .65
23. Hexachlorobiphenyl (3) .66
24. Hexachlorobiphenyl (4) .25
25. Heptachlorobiphenyl (1) 1.51
26. Heptachlorobiphenyl (2) .89
27. Heptachlorobiphenyl (3) .70
28. Heptachlorobiphenyl (4) .97
29. Heptachlorobiphenyl (5) 2.36
Pesticides
1. Triflan(Triflural in) .63
2. g-BHC 1.63
3. Hexachlorobenzene .35
4. 2,4-D, Isopropyl Ester 2.32
5. b-BHC 13.39
6. a-BHC 1.40
7. Heptachlor 2.01
8. Di-n-butyl phthalate
9. Zytron .91
10. Aldrin 1.98
11. DCPA .53
12. Isodrin 2.23
13. Heptachlor epoxide 1.49
14. Oxychlordane 6.69
15. g-Chlordane 1.18
16. o.p-DDE .60
17. Endosulfan I 8.61
18. p,p'-DDE .84
19. Dieldrin 4.63
20. o.p-DDD .57
21. Endrin 2.19
22. Chlorobenzilate 1.12
23. Endosulfan II 13.39
24. o.p-DDT & p.p'-DDD .79
25. Kepone(Chlordecone) 1.80
26. p.p'-DDT 1.27
27. Methoxychlor 1.30
28. Tetradifon 3.89
29. Mi rex -39- 1.04
-------
Volatile Organics
Halomethanes
Dichloromethane .0023
Trichloromethane .0018
Tetrachloromethane .0036
Tribromomethane .0021
Dibromochloromethane .0015
Bromodichloromethane .0018
Trichlorofluoromethane .0063
Chlorinated Ethanes
1,1-Dichloroethane .0044
1,2-Dichloroethane .0042
1,1,1-TMchloroethane .0035
1,1,2-Trichloroethane .004
1,1,2,2-Tetrachloroethane .0031
Chlorinated Ethylenes
1,1-Uichloroethylene .0088
1,2-Dichloroethylene .0047
Trichloroethylene .0026
Tetrachloroethylene .0027
Chlorinated Propanes and Propenes
1,2-Dichloropropane .0051
cis-l,3-Dichloro-l-propene .0032
trans-1,3-Dichloro-1-propene .0027
Aromatics
Benzene .0008
Methyl benzene
Ethyl benzene .001
1,3-Dimethyl benzene .0011
1,2-and 1,4-Dimethylbenzene .001
Chlorobenzene .0012
-40-
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Table 17
Organic Compounds Identified in Sediments by the GC/MS Method:
L'Anse, Michigan, May 23, 1981
(All values are mg/kg dry weight unless otherwise noted)
Location Sample Site Number
Parameter
Benzene
Methyl benzene
Tetrachl oroethyl ene
Di-n-butyl phthalate
Fluoranthene
Pyrene
Chrysene/Benz(a)anthracene
bis(2-Ethylhexyl) phthalate
LAN 81
03
LAN 81
03DUP
LAN 81
04
Volatile Organ ics
.053
1.178
Semi
Base N«
2.72
0.49
.041
1.280
Volatile (
;utral Acic
.009
)rganics
1 Mixtures
1.52
.3
.56
.60
.59
LAN 81
07
.013
.006
.002
.78
-41-
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Table 18
Organic Compounds Tentatively Identified in Sediments by the GC/MS Method:
L'Anse, Michigan, May 23, 1981
(i.e., compounds with high similarity to library mass spectra of the
compound, but not run against actual standards of the compound)
Location Sample Site Number
Parameter
Hydrocarbons
2-Cyclohexen-l-one, Dimethyl
Di ethyl ether
Trichloromethane-L)
LAN 81
03
Semi '
*
Vo
*
*
LAN 81
03 DUP
/olatiles (.
atile Orge
*
LAN 81
04
Jrganics
*
mics
*
LAN 81
07
*
*
*
*Compound tentatively identified in sample from this site.
-42-
-------
References
U.S. Environmental Protection Agency (USEPA) 1984, Methods Manual for Bottom
Sediment Sample Collection, Great Lakes National Program Office, Region
V, Chicago, Illinois
USEPA 1979a. Chemistry Laboratory Manual for Bottom Sediments and Elutriate
Testing, NTIS PB-294596.
USEPA 1979b. Methods for Chemical Analysis of Water and Wastes. Cincinnati
USEPA 60U/4-79-020.
-43-
-------
Appendix A
GUIDELINES FOR THE POLLUTIONAL CLASSIFICATION
OF CRIAT LAKES HARBOR SEDIMENTS
"U.S. EKVIROKMSXIAL PROTECTION AGENCY
REGION V
CHICAGO, ILLINOIS
April, 1977
A-l
-------
Guidelines for the evaluation of Great Lakes harbor sediments, based on bulk
•edixaent analysis, have been developed by Region V of the U.S. Environmental
Protection Agency. These guidelines, developed under the pressure of the need
to »ake immediate decisions regarding the disposal 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
developed.
The guidelines are based on the following facts and assumptions:
1. Sed5ments 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
sucli that the assessment of any sample must be based on all
factors and not on any single paraneter with the exception of
nercury and polychlorinated biphenyls (PCB's).
3. Due to the documented bioaccumulation of mercury and PCB's, rigid
limitations are used vhich override all other considerations.
Sediments are classified as heavily polluted, moderately polluted, or nonpolluted
by evaluating each parameter measured against the scales shown below. The
overall classification of the sample is based on the most predominant classifi-
cation of the individual parameters. Additional factors such as elutriate test
results, source of contamination, particle size distribution, benthic nacroin-
vertebrate populations, color, and odor are also considered. These factors arc
interrelated in a complex manner and their interpretation is necessarily somewhat
subjective.
A-2
-------
Thfc following ranges used to classify sediments from Great Lakes harbors arc
based en compilations of data from over 100 different harbors since 1967.
KONPOLLUTED
Volatile Solids (Z) <5
COD (mg/kg dry weight) <40,000
TKN " " " <1,000
Oil and Grease <1,000
(Hexanc Solubles)
(ing/kg dry weight)
Lead (mg/kg dry weight) <40
Zinc « « « <90
The folloxcins supplementary ranges used
MODERATELY POLLUTED HEAVILY POLLUTED
5-8
40,000-80,000
1,000-2,000
1,000-2,000
40-60
90-200
to classify sediments from
harbors have been developed to the point where they are usable but
eubject to modification by the addition
on 260 samples from 34 harbors sampled
KONPOLLUTED
Aamonfa (eg/kg dry weight) <75
Cyanide " " " <0.10
Phosphorus " " " <420
Iron H » it <17,000
Kickel * it » <2Q
Manganese « « » <300
Arsenic " " " <3
Cadmium " " M *
Chromium ** " " <25
Barium " " " <20
Copper «»«i» <25
of new data. These ranges
>8
>80,000
>2,000
>2,000
>60
>200
Great Lakes
are still
are based
during 1974 and 1975.
MODERATELY POLLUTED HEAVILY POT.' l*TrO
75-200
0.10-0.25
420-650
17,000-25,000
20-50
300-500
.V8
*.
25-75
20-60
25-50
>200
>0.25
>650
>25,000
>50
>500
>8
>6
>75
>60
>50
*Lowcr limits not established
A-3
-------
The guidelines stated below for mercury and PCB's are based upon the best avail-
able Information and ate subject to revision as new information becomes available.
Methylatlon of mercury at levels £ 1 tug/kg has been documented (1,2). Methyl
•ercury 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 veil understood. However, bioaccumulation of PCB's
at levels ^ 10 mg/kg in fathead minnows has been documented (3).
Because of the known bioaccumulation of these toxic compounds, a rigid limitation
Is used. II the guideline values are exceeded, the sediments are classified as
polluted and unacceptable for open lake disposal no matter what the other data
indicate.
POLLUTED
Mercury 21 1 ng/kg dry weight
Total PCB's ^ 10 Eg/kg dry weight
The pollutior.al classification of sediments with total PCB concentrations between
1,0 mg/Ug and 10.0 mg/kg dry weight will be determined on a case-by-case basis.
a. Elutriate test results.
The elutriate test was designed to simulate the dredging and disposal process.
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,
ceotrifugcd, and filtered through a 0.45 u filter. The filtered water (elu-
triate vatcr) is then chemically analyzed.
A-4
-------
A sample of the dredging cite 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 like constituents indicates whether a constituent was or was not released
in the test.
The value of elutriate test results are limited for overall pollutional
classification 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
nore toxic constituent, the elutriate test results can shift the classifi-
cation toward the more pclluted or the less polluted range, respectively.
b. Source of sediment contamination.
In many cases the sources of sediment contamination are readily apparent.
Sediments reflect the inputs of paper mills, steel mills, sewage discharges,
and heavy industry very faithfully. Many sediments may have moderate or
high concentrations of TKN, COD, and volatile solids yet exhibit no evidence
of nan 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 may be given in the range values for TKR, COD, and volatile
solids provided that toxic materials are not also present.
A-5
-------
t. 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 survey
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 pol-
luted 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.
Detritus. Detritus may cause higher values for the organic parameters COD,
TKN, and volatile solids. It usually denotes pollution from natural sources.
Note: The determination of the "naturalness" of a sediment depends upon the
establishment of a natural organic source and a lack of man made pollution
sources vith low values for metals and oil and grease. The presence of
detritus is not decisive in Itself.
A-6
-------
0i)y material. This aloout always comes from industry or shipping activities.
Samples showing visible oil are usually highly contaminated. If chemical
results are marginal, a notation of oil is grounds for declaring the sediment
to be polluted.
d. Benthos.
Classical biological evaluation of benthos is not applicable to harbor or
Channel sediments because these areas very seldom support a well balanced
population. Very high concentrations of tolerant organisms indicate organic
Contamination but do not necessarily preclude open lake disposal of the
•f.dlments. A moderate concentration ex oligochaetes or other tolerant organises
frequently characterizes on acceptable sample. The worst case exists when
there is a complete lack or very limited number of organisms. This cay
indicate a tPxic condition.
Jn addition, biological results must be interpreted in light of the habitat
provided in the harbor or channel. Drifting sand can be a very harsh habitat
Vhlch may support only a few organisms. Silty material, on the other hand,
Usually provides a good habitat for sludgeworms, leeches, fingernail clacs,
«nd perhaps, amphipods. Material that is frequently disturbed by ship's
propellers provides a poor habitat.
A-7
-------
REFERENCES
1. Jensen, S., and JernclSv, A., "Biological Kethylation of Mercury in Aquntic
Organisms," Nature, 223, August 16, 1969 pp 753-754.
2. Magnuson, J.J., Forbes, A., and Hall, R., "Final Report - An Assessment of
the Environmental Effects of Dredged Material Disposal in Lake Superior -
Volume 3: Biological Studies,*' Marine Studies Center, University of
Wisconsin, Madison, March, 1976.
3. Baiter, 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, Tennessee
-------
TECHNICAL REPORT DATA
'itsst rcaJ Inw/cnoin on thi rcicrsi btfort. complrttnpi
1 REPORT NO
EPA905/4-84-003
•5 TITLE. AND SUBTITLE
GLNPO Harbor Sediment Program
Lake Superior 1981:
Ashland, Wisconsin
Black River. Michigan. L'Anse. Michigan
3 RECIPIENT'S ACCESSIOr+NO.
5 REPORT DATE
April 1984
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO.
Anthony G. Kizlauskas, David C. Rockwell,
Roger E. Claff
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Great Lakes National Program Office
U.S. Environmental Protection Agency
536 S. Clark St., Chgo., IL 60605
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
Great Lakes National Program Office
U.S. Environmental Protection Agency
536 S. Clark St.^ Chgo.. IL 60605
13. TYPE OF REPORT AND PERIOD COVERED
FTMAI
14. SPONSORING AGENCY CODE
Great Lakes Natinoal Program
Office - USEPA. Region V
15. SUPPLEMENTARY NOTES
Undertaken as part of the Great Lakes National Program Office, Harbor Sediment
Program
16. ABSTRACT
This report presents sediment chemistry data from three Lake Superior harbors
sampled May 21-23, 1981.
Sediment from three of five locations sampled in Ashland, Wisconsin was analyzed:
At the sewage treatment plant outfall, sediment had moderate pollutant levels
overall, with elevated levels of total phosphorus, mercury and PAH's.
Sediments were mostly coarse material with only a thin veneer of silt and
and organics, so the contamination was probably of recent origin. Sediment at the
power plant outfall had elevated nutrient and metals levels, and trace PAH's.
High organic content may have been largely responsible for metals levels. Sediment
at the mouth of a small stream was mostly sand and had low pollutant levels.
One sediment sample of five locations sampled at Black River, Michigan was
analyzed. Generally low levels of organic and inorganic pollutants, with moderate
levels of phosphorus and manganese were detected.
There sediment samples chosen from eight locations at L'Anse Michigan were analyzed.
The sediment was composed of sand, or sand with some silt. Generally low levels of
organic and inorganic pollutants were found, with moderate levels of T.K.N.. C.O.D.
17.
and copper.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS C. COS AT I Field/Group
Sediment
Organic Pollutants
Inorganic Pollutants
Polyaromatic Hydrocarbons (PAH's)
Phosphorus
Mercury
Lake Superior
Ashland, Wisconsin
Black River, Michigan
L'Anse, Michigan
13. DISTRIBUTION STATEMENT
Document is available through the National
Technical Information Service, Springfield
Virginia 22161
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OF PAGES
59
20 SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
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