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EPA-905/4-86-001
March 1986
Report on an Investigation of Sediment Contamination
The Milwaukee Estuary, Wisconsin
Sampled July 29-31, 1980
Prepared by
Anthony G. Kizlauskas
Remedial Programs Staff
Great Lakes National Program Office
United States Environmental Protection Agency
For
GLNPO Report #86-01
Great Lakes National Program Office
United States Environmental Protection Agency
536 South Clark Street
Chicago, Illinois 60605
October 1982
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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
of commercial products constitute endorsement or recommendation for use.
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Table of Contents
Foreword i i i
List of Exhibits iv
I. Summary 1
II. Conclusions 2
III. Sediment Survey of July 29-31 , 1980 3
A. Sampling Methods 3
B. Analytical Methodology and Problems Encountered 6
C. Results and niscussion 9
Field Observations 9
Pollutant Concentrations 10
Conventional Pol 1 utants 11
Me tal s 15
Organic Priority Pollutants 17
IV. Comparison with Historical Sediment Data 20
References 22
Appendix A - Field Observations and Chemistry Data from 23
July 29-31, 1980, USEPA Milwaukee Estuary
Sediment Study
Appendix B - Guidelines for the Pollutional Classification 48
of Great Lakes Harbor Sediments, USEPA, Region V,
Chicago, Illinois, April, 1977
n
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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
U.S. actions in fulfillment of the Great Lakes Water Quality Agreement of
1978 between Canada and the United States of America.
m
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TABLES
Page
1. Sample Sites - Milwaukee Estuary, July 29-31, 1980 4
2. Analytical Methodology 7
3. Summary of Apparent Source Areas for Various Contaminants 11
A. Bo ri ng Log 24
B. Sample Numbers Used in this Report and the Sampling 28
Location and Depth Interval they Represent
C. Sediment Concentrations of some Conventional Pollutants 30
and Metals in the Milwaukee Harbor Estuary
July 29-31 , 1980
D. Organic Compounds Sought and Typical Detection Limits 38
E. Sediment Concentrations of some Organic Pollutants in 40
the Milwaukee Harbor Estuary July 29-31, 1980
FIGURES
1. Sediment Sampling Sites, July 29-31, 1980 5
2. Typical Variation in Sediment Pollutant Concentration 14
July 29-31 , 1980
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I. SUMMARY
The sediment samples collected in the Milwaukee Estuary on July 29-31,
1980 show low to moderate levels of organic contaminants and moderate
to high levels of inorganic contaminants. The results show similar
levels of polychlorinated biphenyls (PCB) contamination as was found
in previous surveys of the same areas. Although increases in PCB
levels with depth in the sediment column were found at some sites, no
pockets of severe PCB contamination were found in the 1980 study area.
Polynuclear aromatic hydrocarbons were found to be at low to moderate
levels in this survey.
The quality control, sample analysis'procedures, and analytical results
for the data were reviewed for reasonableness and consistency. The data
was judged to be acceptable on the basis of the review.
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II. CONCLUSIONS
1. Sediments in the Milwaukee Estuary contain high concentrations of
conventional inorganic pollutants and heavy metals, and detectable
levels of a number of organic priority pollutants.
2. Contaminant levels are generally highest in the upper sediment
layers, indicating probable recent input of pollutants to the
Estuary.
3. Major source areas of pollutants appear to be; upstream of 25tn
Street on the Menomonee River, the Menomonee Canal , the Jones
Island STP, and on the Kinnickinnic River between Kinnickinnic
Avenue and the Kinnickinnic Basin.
4. There are few direct industrial process discharges into the
Milwaukee Estuary. Most such discharges are directed to the
Jones Island Municipal Sewage Treatment Plant (STP) by sanitary
sewers. During rainfall events, it is possible that process
wastes mixed with storm water are discharged directly to the
Estuary through combined sewer overflow (CSO).
5. Contaminants that are apparently due primarily to combined sewer
overflow discharges include phosphorus throughout the Estuary,
polynuclear aromatic hydrocarbons (PNAs) on the Milwaukee River
between Walnut Street and St. Paul Avenue, and polychlorinated
biphenyls (PCBs) on the Kinnickinnic River.
6. Sediment PCB levels have remained constant since the mid 1970's.
Although sediment PCB levels did increase with depth in the
sediment column at some sites, there were no pockets of severe
contamination found in the 1980 study areas. However, based
upon sampling by others, PCB concentrations are likely to exceed
50 mg/kg in portions of the outer harbor.
7. The nature and degree of sediment contamination in the Estuary is
comparable to major industrialized Great Lakes harbors subject
to large numbers of direct industrial discharges.
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III. SEDIMENT SURVEY OF JULY 29-31. 1980
Previous sediment surveys in the Milwaukee Fstuary showed significant
sediment contamination with a wide range of pollutants. However, the
studies were limited in scope and in pollutants measured, and/or were
surface grab samples only. Contaminant concentrations in sediments can
be highly variable with depth. The deeper (older) sediments are often
more contaminated as of results of historical , less stringently regulated
discharges than are the surface (recent) discharges. In order to better
define the nature (kinds of pollutants) and extent (variation with
depth and along the rivers) of sediment contamination in the Milwaukee
Estuary, the USEPA Great Lakes National Program Office (GLNPO) contracted
with the University of Wisconsin Milwaukee, Center for Great Lakes
Studies (CGLS) to collect sediment core samples at 23 representative
locations (Figure 1 and Table 1) within the Estuary. The samples were
collected in the period, July 29-31, 1*980.
The samples were analyzed by Envirodyne Engineers, St. Louis, Missouri
under contract to the USEPA Central Regional Laboratory (CRL), Region V.
A. SAMPLING METHODS
Sediment core samples were obtained utilizing the CGLS RV Neeskay on
July 30 and 31, 1980. On July 29, 1980, a Boston Whaler was used up-
stream of St. Paul Avenue (sample sites 14-16) on the Milwaukee River
and upstream of Rogers Street on the Kinnickinnic River (sampling site
10) to allow passage under stationary bridges too low for the Neeskay
to pass under. Only surface grab samples were collected from the
Boston Whaler due to the weight and unwieldiness of the core sampler.
Grab samples were collected with a Wildco Mo. 1725 610 sampler. Core
samples were collected with a Benthos No. 2171 gravity corer equipped
with a stainless steel nosecone, core catcher, and liner (2-1/2" I.D.),
all of which were rinsed with analytical grade n-hexane prior to
sampling. The core samples were extruded in 30 cm (approximately 1 ft.)
lengths into glass containers that had been previously rinsed with
hexane. Aluminum foil was placed over the container mouths prior to
closure. The samples were stored in a refrigeration unit at or near
4°C prior to transport to the CRL in Chicago. The samples were
transferred to well-insulated blood storage boxes with ice for the two
hour drive to Chicago.
Pertinent sample information and general observations were recorded in
a boring log. 35mm color slides were taken of the vicinity of each
sampling site to aid in sampling site documentation. EPA chain-of-
custody procedures were employed (NPDES Compliance Sampling Inspection
Manual MCD-51 , USEPA).
For sampling quality control purposes, replicate cores were taken in
close proximity at sites 7 and 11.
Samples from sites 14, 16, 20, and the 60-90 cm section from the site
19 sample were lost in a handling accident at the CRL while they were
being prepared for shipment to the contractor for analysis. There are,
therefore, no chemical analyses available for those samples.
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TABLE 1
Sample Sites - Milwaukee Estuary, July 29-31, 1980
Sample Site Number Description
1 Outer Harbor
2 Near Jones Island Sewage Treatment Plant Outfall
3 Inner Harbor Entrance Channel at Daniel Webster
Hoan Bridge
4 Milwaukee River and Kinnickinnic River Confluence
5 Kinnickinnic River at Greenfield Avenue
6 Central Kinnickinnic Basin
7 North East End of Kinnickinnic Basin
8 Kinnickinnic River at Kinnickinnic Avenue
9 Kinnickinnic River at Rogers Street
10 Kinnickinnic River at Lincoln Avenue
11 Milwaukee River at Florida Street
12 Milwaukee River at Menomonee River Confluence
13 Milwaukee River at St. Paul Avenue
14 Milwaukee River at Highland Avenue
15 Milwaukee River at Walnut Street
16 Milwaukee River at Humboldt Boulevard
17 Confluence of Menomonee River and Menomonee Canal
18 Confluence of Menomonee Canal and Burnham Canal
19 Menomonee Canal at 11tn Street
20 Burnham Canal at 10th Street
21 Menomonee River at 7tn Street
22 Menomonee River at Muskego Avenue
23 Menomonee River at 25tn Street
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MILWAUKEE
i
141
LAKE
MICHIGAN
23 22-421-17
KINNICKINNIC
=====
RIVER
FRANCIS
Figure 1. Sediment Sampling Sites
July 29-31, 1980
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B. ANALYTICAL METHODOLOGY AND PROBLEMS ENCOUNTERED
The analytical methods employed for this study are outlined in Table 2.
This section contains a discussion of the problems encountered in
employing each of the analytical methods.
Chemical Oxygen Demand (COD)
The only difficulty that was encountered during this analysis was the
observance of high concentrations in most of the samples. This problem
was overcome by using only 0.2g of sample for the analysis which put
most of the samples within the analytical range.
Total Phosphorus
Problems were encountered with color stability using the 2-reagent
ascorbic acid method. Although this method claims that the color
should be stable after five minutes and good for one hour, the analyst
found that the color kept deepening beyond the five minute period.
To overcome this problem, the analyst switched to a stannous chloride
method and used 5 ml of ^$04 as suggested by the USEPA task officer.
The ascorbic acid method had been used during the analysis of the first
10 percent of the samples. Since these results appeared to be higher
than expected due to the instability of the color using this method,
the samples were rerun using the stannous chloride method. The
earlier results were discarded.
The perchloric acid digestion was not used during the analysis due
to the lack of a hood for safe performance of this procedure. The
modification had been cleared with the USEPA task officer during his
site visit. Further, 5 ml rather than the 1 ml of sulfuric acid
suggested in the agreed-upon method was employed. This modification
was found to give a better recovery on the NBS standard sediment.
Ammonia
Problems were encountered with precipitate formation and low re-
coveries during analysis of the first 10 percent of the samples. The
laboratory at that time switched to the automatic method referenced
in Table 2. Because of the better quality control (OC) results
obtained with this method, the first 10 percent of the samples were
reanalyzed using the latter method and earlier results discarded.
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TABLE 2
ANALYTICAL METHODOLOGY
TKN
Ammonia
Total Solids
Volatile Solids
COD
Phosphorus
Cyanide
Phenol
Oil & Grease
Metals
Mercury
Pesticides/PCB's
Acid,
Base/Neutral,
Organic Priority
Pollutants
CLM*
CLM*
CLM*
CLM*
Chemistry Laboratory Manual for
Bottom Sediments, Great Lakes Region
December 1969
Standard Methods, 14th Edition
Method 425E
CLM*
CLM*
CLM*
CLM*
Methods for Chemical Analysis of
Water and Waste, EPA, March 1979
No. 245.5
Extraction by CLM* Followed by
Cleanup using EPA Method #608,
Federal Register, December 3, 1979
CLM*
Page 43
Page 36
Page 3
Page 5
Page 5
Page 479
Page 25
except manual
colorimetric
measurement
Page 90
Page 103
Page 69
Page 69
Page 108
Page 140
*CLM - Chemistry Laboratory Manual for Bottom Sediments and Elutriate
Testing, EPA-905/4-79-014, USEPA, Region V, March 1979
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Total Kjeldahl Nitrogen (TKN)
The methodology employed for this analysis was also changed from a manual
to the automated method listed in Table 2. This was found to produce
much better results on the NBS standard sediment sample as well as results
in the range anticipated by EPA. For this reason, the first 10 percent of
the samples were rerun using the automatic method and the earlier results
discarded.
Phenols
High spike recoveries were encountered during this analysis. This may be
due to a slight variation in the logistics of running the samples versus
the spikes. Samples were manually distilled and the distillates held
until a complete set was available to be put on the Technicon. However,
the spikes were distilled and run immediately. The high spike recoveries
may, therefore, be due to loss of phenols in the distillates during storage.
Cyanide
In reviewing the data for the first 10 percent of the samples, it was noted
that these were calculated incorrectly. The correct data are reported in
this report.
Metals
Standard additions were found to be necessary on all samples in the first
batch of samples analyzed. Because of matrix variations, however, standard
additions were found to be necessary in only 30-40 percent of the remaining
samples in which high organic interferences were encountered.
Spike recoveries on some of the samples fall slightly outside of the per-
scribed range. This is probably due to the inaccuracy introduced by dilution
of the samples and spikes in order to put them within the analytical range.
Dilution was found to be necessary on almost all samples being analyzed for
selenium, arsenic, manganese, cobalt and zinc.
Mercury analyses were all performed in duplicate, the reported value being
the average of the two determinations.
Pesticides/PCB's
High sulfur interferences were encountered in most samples, requiring that
most samples be treated two to three times with mercury or copper to
eliminate the interferences. In addition, most samples had to be run
at more than one dilution even after florisil cleanup due to high back-
ground levels. Pesticide analyses were not confirmed by GC/MS.
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Gas Chromatography/Mass Spectrometry (GC/MS)
Almost all of the samples analyzed were found to be extremely dirty, creating
problems with both their preparation and the analysis. Emulsions were en-
countered in almost all cases during the base/neutral acid-washing separation
procedure. Concentrations were found to take additional time and several
samples could not be reduced to the level specified in the method because
of the high organic content.
Instrumental problems were a result of the high hydrocarbon backgrounds en-
countered which made it difficult to identify and quantify the priority
pollutants as well as to perform the library searches. Although the Quantid
program was employed for the priority pollutants, it was found to not always
be capable of picking out the peaks of these compounds. This was also
probably due to the high backgounds encountered and mandated some manual data
reduction to assure the accuracy of the analysis.
C. RESULTS AND DISCUSSION
FIELD OBSERVATIONS
Field observations made on the sediment samples as they were collected were
recorded in a boring log (Appendix A, Table A). Sediments in the Milwaukee
River upstream of St. Paul Avenue were described as mud or muddy sand with
organic detritus, having an earthy odor. Sediments in the vicinity of St.
Paul Avenue had an oily odor. Sediments at the junction of the Milwaukee
River and Menomonee River were grey clay indicating a scoured (non-deposit-
ional) area. Sediments in the Menomonee River, Menomonee Canal, and the
Burnham Canal were described as black mud over grey clay having a hydrocarbon
and/or disagreeable odor. Sediments in the Kinnickinnic River upstream of
Kinnickinnic Avenue were described as mud with an earthy odor, while sedi-
ments further downstream were characterized as having an oily/hydrocarbon
odor. Sediments in the Milwaukee River downstream of the Menomonee and
Kinnickinnic River junctions, in the Inner Harbor Entrance Channel were
described as dark gray to black mud with an earthy odor. Hard grey clay
was found at sample site 1 in the Outer Harbor indicating a scoured area.
Sediments adjacent to the Jones Island Municipal Sewage Treatment Plant
(STP) were found to have a stale odor.
Based upon the field observations, it appears that the major sources of
petroleum contamination of the sediments are situated: along the Menomonee
River beginning upstream of 25tn Street; along the Menomonee Canal; along
the Burnham Canal; on the Kinnickinnic River downstream of Rogers Street;
and in the Kinnickinnic Basin vicinity. The degraded sediment conditions
at St. Paul Avenue on the Milwaukee River are probably from an upstream
source or sources on the Menomonee River (see following discussion under
oil and grease).
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POLLUTANT CONCENTRATIONS
Unlike the case of a deep lake depositional area, sediments in the estuary
rivers are not likely to have been deposited in a vertically sequential
manner (new sediments always covering the older sediments) due to distur-
bances from dredging and resuspension from navigation, CSO discharges,
storm water flows, and flow augmentation of the Milwaukee River and
Kinnickinnic River via flushing tunnels. The estuary has very complex
hydraulics due to the interaction of the three rivers and Lake Michigan.
Wisconsin Electric Power Company (WEPCO) withdraws cooling water (about
250 cfs) from the Menomonee River near South 10t'1 Street (extended) and
discharges heated water to the South Menomonee Canal. Since the average
flow of the Menomonee River is only about 90 cfs, water is often drawn
upstream along the bottom from Lake Michigan and the Milwaukee River
(Harleman and Stolzenbach, 1967). Thus, the vertical sediment profile
most likely does not accurately represent a time history of sediment
deposition. Also, sedimentation rates within the estuary are likely
to be highly variable between locations.
Therefore, rather than comparing pollutant concentrations from a particular
strata (0-30 cm, 30-60 cm, etc.,) for all the sites sampled, it seemed more
appropriate to compare the maximum concentrations at each sampling site.
The following discussion of variations in pollutant concentrations within
the estuary is based on this type of a comparison. Using this approach
produced rather consistent patterns in pollutant variation within the
estuary, whereas earlier investigations (Rexnord, 1979) generally reported
similar concentrations throughout the estuary. It should be noted that
these studies did find differences between the river sediments upstream of
the estuary and those within the estuary, which was the primary purpose of
those investigations. The apparent source areas for various pollutants
based upon the patterns observed in the sediments are summarized in Table 3
and discussed below.
Sites 1 and 12 were scoured and generally had low pollutant concentrations.
The discussion will, therefore, omit these sites unless something unusual
was found. Overall contaminant levels are highest within the upper 60 cm
of the core samples. Therefore, only exceptions to this will be noted
in the discussion. It should be noted, however, that since compaction
factors (i«e. depth of sediment penetrated v_£ length of sediment column
retrieved in core barrel) were not determined, it is not known whether
this 60 cm of sediment in the core tube represents 60 cm of in-place
sediment or a much greater amount. Additionally, since no dating of the
sediments was done and deposition rates are unknown, it is not possible
to determine how recent the sediments in the top 60 cm are. However, the
vertical variation observed indicates a probable recent input of pollutants
to the estuary. Site 2 is located just off the Jones Island Sewerage Treat-
ment Plant (STP) outfall. The STP is likely the source of much of the
sediment contamination at that site. However, some of the contaminants
may also be the result of sediments from the other estuary rivers settling
out in the Outer Harbor, where there is a sudden decrease in velocity
from that in the Inner Harbor Entrance Channel.
10
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TABLE 3
Summary of Apparent Source Areas for Various Contaminants
Area
Contaminants
Milwaukee River
Upstream of Walnut Street
Upstream of St. Paul Avenue
Jones Island STP
CSOs (throughout)
CSOs (Walnut Street to
St. Paul Avenue)
Phenols
PNAs
Oil and Grease, Phosphorus, Ammonia,
TKN, Volatile Solids, COD, Phenols,
Metals, Cyanide, Selenium, PCBs, PCP,
Heptachlor, Phthalates, 2,4-dinitrotoluene
Phosphorus
PNAs
Menomonee River
Upstream of 25th Street
25th Street to Muskeyo Avenue
Upstream of 7tn Street
Menomonee Canal
Menomonee Canal/Burnham Canal
Junction
Menomonee River/Menomonee Canal
Junction
CSOs (throughout)
Oil and Grease, Ammonia, TKN, Volatile
Solids, COn, Metals, Phthalates, PNAs
Phenols, Cobalt
PCBs, Cyanide
Oil and Grease, Ammonia, TKN, Volatile
Solids, COD, Metals, Phthalates
Tin
Tin
Phosphorus
Kinnickinnic River
Upstream of Lincoln Avenue
Upstream of Kinnickinnic Avenue
Kinnickinnic Basin
CSOs (throughout)
Phenols
Oil and Grease, Volatile Solids, COD,
Metals, Phthalates, PNAs
Oil and Grease, Ammonia, TKN, COD,
Volatile Solids, Metals, Cyanide,
PNAs, Naphthalene
Phosphorus, PCBs
11
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Table B in Appendix A lists the correspondence between particular samples
from the various cores and the sample numbers used in the analytical data
tables.
In the following discussion, qualitative terms such as "low", "moderate",
"high", etc., are based upon the author's experience with Great Lakes
sediment data and the April 1977 EPA, Region V, "Guidelines for the
Pollutional Classification of Great Lakes Harbor Sediments" (Appendix B).
CONVENTIONAL POLLUTANTS
Table C in Appendix A contains the analytical data from conventional
pollutants and metals from the July 29-31, 1980 study.
Oil and Grease
Oil and grease levels were very high throughout the study area, ranging
from about 4,000 to 15,000 mg/kg.
In the Milwaukee River, oil and grease levels were highest at St. Paul
Avenue (15,000 nig/kg), decreasing both upstream and downstream of that
point.
Oil and grease levels in the Menomonee River and Menomonee Canal were the
highest in the study area, ranging up to 23,300 mg/kg. Concentrations
generally decreased with distance downstream in the river and canal.
Sediment oil and grease concentrations in the upstream portion of the
Kinnickinnic River were the lowest in the study area (2,420 to 4,940 mg/kg),
Concentrations increased downstream and were highest in the vicinity of
Kinnickinnic Avenue and in the Central Kinnickinnic Basin (15,900 and
16,400 mg/kg, respectively). Sediment oil and grease levels peaked again
off of the Jones Island STP (14,400 mg/kg). This spatial variation of
pollutant concentrations was found to be common of most pollutants. This
pattern, shown in Figure 2, will be referred to as the "typical" pattern in
the remainder of this report.
Based on the data, sources of oil and grease appear to be located on the
Menomonee River at or upstream of 25^n Street, on the Menomonee Canal,
on the Kinnickinnic River in the area between Kinnickinnic Avenue and the
Kinnickinnic Basin, and the Jones Island STP.
The high oil and grease levels on the Milwaukee River at St. Paul Avenue
could be explained by three different machanisms: (a) There is a source
(CSO, point source) in the vicinity of St. Paul Avenue, (b) There is an
upstream source on the Milwaukee River, but the hydraulic characteristics
of the Lake Michigan/Milwaukee River interaction result in a net flow
minimum in the vicinity of St. Paul Avenue, resulting in the suspended
contaminants from upstream settling out in this area, (c) The hydraulic
characteristics of the Milwaukee River/Menomonee River/WEPCO power plant
intake and discharge interaction are such that contaminated sediments
originating from the Menomonee River are transported upstream into the
12
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Milwaukee River, reaching St. Paul Avenue, where the net flow in the
Milwaukee is near zero, causing high rates of deposition in that area.
Such flow reversals have been found to occur (Gruber, 1981). It is
most likely that the actual situation is a complex combination of
all three mechanisms operating in concert.
Total Phosphorus
Phosphorus levels throughout the Estuary were very high. The typical range
was from 500 to 1,500 mg/kg. The highest sediment total phosphorus levels
(8,250 mg/kg) were found near the Jones Island STP, followed by the St. Paul
Avenue site on the Milwaukee River (2,630 mg/kg).
Phosphorus concentrations did not follow the typical pattern of spatial
variation. Phosphorus levels in all three .rivers tended to increase
proceeding downstream, probably due to the cumulative effects of CSO
discharges. Based on the data, the primary sources of phosphorus appear
to be CSOs and the Jones Island STP discharge.
Ammonia
Sediment ammonia levels in the Estuary were high, typically ranging from
200 to 400 mg/kg. The spatial distribution of ammonia concentrations
followed the typical pattern (Figure 2). In the Milwaukee River, ammonia
levels increased from Walnut Street to St. Paul Avenue. Ammonia levels
in the Menomonee River and Menomonee Ca-nal decreased proceeding downstream.
The highest ammonia levels (1,250 mg/kg) were found in the upstream-most
samples on the Menomonee River. Ammonia concentrations increased proceeding
downstream on the Kinnickinnic River toward the Kinnickinnic Basin. Based
on the data, the principal sources of ammonia appear to be located up-
stream of 25tn Street on the Menomonee River; along the Menomonee Canal; in
the vicinity of the Kinnickinnic Basin; and the Jones Island STP.
Total Kjeldahl Nitrogen
Total Kjeldahl nitrogen (TKN) levels were high in the Estuary, typically
ranging from 1,500 to 3,000 mg/kg. The spatial distribution of sediment
TKN followed the typical pattern (Figure 2). The highest TKN levels
(7,680 mg/kg) were found in the samples from 25tn Street on the Menomonee
River.
Total Volatile Solids
Total volatile solids (TVS) levels were high, typically ranging from 10 to
15 percent. TVS levels followed the typical pattern of spatial variation
(Figure 2). The highest TVS levels were in the lower half of the core
from site 12 (Milwaukee River and Menomonee River confluence (19.2%)) and
off of the Jones Island STP (16.8%). There is no apparent reason for the
high TVS level at site 12, since levels of most other pollutants were very
low at this scoured site.
13
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MILWAUKEE
RIVER
LAKE
MICHIGAN
DECREASING-
MENOMONEE
RIVER
ST.
FRANCIS
Figure 2. Typical Variation in Sediment
Pollutant Concentration
July 29-31, 1980
14
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Chemical Oxygen Demand
Sediment chemical oxygen demand (COD) levels were moderate in the Estuary,
typically ranging from 40,000 to 60,000 mg/kg. The highest COD levels
were found at 25™ Street on the Menomonee River (175,000 mg/kg) and
at the Hoan Bridge in the Inner Harbor Entrance Channel (148,000 mg/kg).
The pattern of COD concentration followed the typical spatial pattern
(Figure 2).
Phenols
Levels of phenols typically varied from 0.2 to 0.5 mg/kg. The highest
levels were found on the Menomonee River at Muskego Avenue (3.51 mg/kg)
and off the Jones Island STP (2.63 mg/kg). The distribution of phenols
appeared to be more random than that of the other pollutants discussed
so far.
Based on the data, sources of phenols appear to be located upstream of
Walnut Street on the Milwaukee River; between 25th Street and Muskego
Avenue on the Menomonee River; upstream of Lincoln Avenue on the
Kinnickinnic River; and at the Jones Island STP.
Cyanide
Sediment cyanide levels were an order of magnitude higher in the Central
Kinnickinnic Basin (36.7 mg/kg) than the levels typical of the rest of
the Estuary (3 to 5 mg/kg). Cyanide levels were lowest in the Milwaukee
River and upstream of Rogers Street on the Kinnickinnic River. Inter-
mediate cyanide levels (6 to 12 mg/kg) were found off of the Jones Island
STP and upstream of 7th Street on the Menomonee River.
METALS
Sediment metals concentrations followed the typical pattern of spatial
variation depicted in Figure 2.
Mercury
Sediment mercury levels in the Estuary were high, typically ranging from
0.5 to 1.0 mg/kg. The highest mercury levels were found in the Menomonee
Canal (up to 2.96 mg/kg); at St. Paul Avenue on the Milwaukee River
(2.39 mg/kg); and off of the Jones Island STP (2.30 mg/kg).
Lead
Sediment lead levels were very high, typically varying between 300 and
500 mg/kg. Concentrations were highest at 25*'1 Street on the Menomonee
River (1,180 mg/kg) and at Kinnickinnic Avenue on the Kinnickinnic River
(1,080 mg/kg).
15
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Cadmium
Sediment cadmium levels were high, typically ranging from 10 to 20 mg/kg.
The highest cadmium levels were found off of the Jones Island STP
(73.7 mg/kg), in the Central Kinnickinnic Basin (45.7 mg/kg), and at
25th Street on the Kinnickinnic River (34.4 mg/kg).
Chromium
Sediment chromium levels were very high in the Estuary, typically varying
between 200 and 500 mg/kg. The highest levels were found off of the Jones
Island STP (2,380 mg/kg) and at St. Paul Avenue on the Milwaukee River
2,250 mg/kg).
Arsenic
Sediment arsenic levels were very high, typically ranging from 15 to 40 mg/kg.
The highest concentrations of arsenic were found in the Central Kinnickinnic
Basin (69.4 mg/kg), off of the Jones Island STP (45.2 mg/kg), at 11th Street on
the Menomonee Canal (44.7 mg/kg), at Muskego Avenue on the Menomonee River (42.5
mg/kg), and in the Outer Harbor (site 1) (41.8 mg/kg).
Zinc
Sediment zinc concentrations in the Estuary were high, typically ranging from
400 to 700 mg/kg. The highest zinc concentrations were observed off of the
Jones Island STP (1,950 mg/kg), in the Central Kinnickinnic Basin (1,730 mg/kg),
and at 25th Street on the Monomonee River (1,140 mg/kg).
Copper
Sediment copper levels were high in the Estuary, typically varying between
100 and 200 mg/kg. Copper concentrations were highest (about 300 mg/kg)
at 25th Street on the Menomonee River, at 11th Street on the Menomonee
Canal, in the Central Kinnickinnic Basin, and off of the Jones Island STP.
Manganese
Moderate to high levels of manganese were found in the Estuary sediments,
typically varying between 400 and 700 mg/kg. The highest levels of
manganese were observed in the Menonomee River from 25tn Street to 7tn
Street (800 to 1,200 mg/kg), in the Milwaukee River between the Menomonee
River junction and Florida Street (800 to 900 mg/kg), and in the
Kinnickinnic River at Greenfield Avenue. In all of the areas just listed,
the highest concentration of manganese were from the lower (older) sediment
deposits in the core, this is in contrast with results found for most other
pollutants, particularly at sites 5 and 11 (Kinnickinnic River at Greenfield
Avenue and Milwaukee River at Florida Street, respectively), where surface
concentrations for most other pollutants were typically much higher than
those deeper in the core. Also, in contrast to other pollutants, manganese
levels were high at the Milwaukee River/Menomonee River junction which is a
non-depositional area. The above leads to the conclusion that the high
manganese levels may be due to naturally high levels in the Estuary sediments.
16
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Tin
Concentrations of tin in the sediments of the Estuary typically ranged
from 20 to 30 mg/kg. The highest levels of tin were observed at St.
Paul Avenue on the Milwaukee River (114 mg/kg), at the confluence of
the Menomonee River and Canal (97.9 mg/kg), off the Jones Island STP
(65 mg/kg), and at the confluence of the Menomonee and Burnham Canals
(64.3 mg/kg). The pattern for tin in the Menomonee River departs from
that of the typical variation. Tin levels were highest downstream in
the Menomonee River/Canal junction area, whereas, for other pollutants,
levels typically dropped off in that area from their upstream concen-
trations. This indicates a possible source of tin in the lower Menomonee
River/Menomonee Canal area.
Cobalt
Cobalt levels in the Estuary sediments typically varied between 5 and 10
mg/kg. Cobalt levels at Muskego Avenue on the Menomonee River (23.8
mg/kg) are much higher than anywhere else in the Estuary, indicating a
possible source of cobalt in this area.
Selenium
Sediment selenium levels were less than the laboratory's analytical
detection limit of 2 mg/kg throughout the Estuary except off of the Jones
Island STP (5.53 mg/kg) and in the Outer Harbor (Site 1) where selenium
was just about the analytical detection limit, indicating the Jones Island
STP as the most likely source of the selenium.
ORGANIC PRIORITY POLLUTANTS
Table D of Appendix A shows organic compounds that were sought and their
typical detection limits. Actual detection limits varied somewhat from
sample to sample depending upon levels of interferences in the particular
sample for the particular compound being sought. For easier data display,
the organic pollutants data (Table E of the Appendix) only shows compounds
that were found at concentrations in excess of the detection limit.
Polychlorinated Biphenyls (PCBs)
Sediment PCB concentrations in the Estuary typically ranged from 2 to
5 mg/kg total PCBs. The highest PCB concentrations were found off the
Jones Island STP (47 mg/kg) and at St. Paul Avenue on the Milwaukee River
(32 mg/kg). The patterns for PCBs on the Menomonee River and Kinnickinnic
River were different from the typical pattern of spatial variation
(Figure 2).
On the Kinnickinnic River, sediment PCB concentrations were essentially
constant in the study area, averaging around 5 mg/kg, with a somewhat
higher concentration in the northeast corner of the Kinnickinnic Basin
(10.22 mg/kg). PCB concentrations were highest at the surface. This
seems to indicate a continuing, diffuse source, either nonpoint or CSO,
on the Kinnickinnic River, and perhaps a source in the Kinnickinnic Basin.
17
-------
On the Menomonee River, sediment PCB concentrations were low at 25tn Street
(1.3 mg/kg) and decreased with depth in the core, indicating the probable
absence of either a present or past source upstream of that point. PCB
concentrations averaged 3 to 4 mg/kg on the river, except for a rise to
around 10 mg/kg in the surface sediments at 7tn Street, indicating a
possible localized source in that vicinity, with otherwise diffuse
sources in the river.
On the Menomonee Canal, PCB concentrations increased from 5.5 mg/kg at
lit" street to 8.5 mg/kg at the junction of the Menomonee and Burnham
canals. At the junction, PCB levels increased with depth, being 3 mg/kg
at the surface and 8.5 mg/kg at depth, indicating past contamination
from a source that has since been curtailed or eliminated.
Other Organic Priority Pollutants
Select samples were chosen for additional organic GC/MS scans (base
neutral, acid, and pesticide fractions) based upon the field observations
(odor, oil, color, sediment type). Those chosen were generally those
that would be expected to have higher levels of contamination, the pur-
pose being to characterize average worst-case levels of contamination
in the Estuary sediments.
Pesticides
Pesticides were only detected in the area from the Outer Harbor to the
Milwaukee/Kinnickinnic River confluence, and at 25*n Street on the
Menomonee River, and then usually only in trace amounts. The exceptions
were: 1.1 mg/kg of heptachlor were detected off the Jones Island STP
and 2.1 mg/kg of toxaphene-like components were detected at the Milwaukee/
Kinnickinnic River confluence. The pattern suggests some pesticides
contamination coming from upstream in the Menomonee River and from the
Jones Island STP.
Phenolic Compounds
Phenolic compounds were not detected in the Estuary sediments except for
trace amounts of 2,4-dimethylphenol at St. Paul Avenue on the Milwaukee
River and at lltn Street in the Menomonee Canal, and a high concentration
of pentachlorophenol (4.5 mg/kg) off the Jones Island STP. Pentachloro-
phenol (PCP) has been previously detected in sludge from the Jones Island
STP (Milwaukee Metropolitan Sewage District, 1981).
Phthalates
Trace levels of several phthalates were detected in virtually all samples.
Bis (2-ethylhexyl) phthalate (DEHP) was detected at higher concentrations,
typically varying between 5 and 15 mg/kg. Levels of this phthalate were
invariably highest in the surface sample from each core. The concen-
trations of DEHP were highest off the Jones Island STP (43 mg/kg) and at
25th Street on the Menomonee River (41.3 mg/kg). The spatial distribution
of concentrations of DEHP follows the typical pattern (Figure 2).
18
-------
Polynuclear Aromatic Hydrocarbons
A number of compounds in the polynuclear aromatic (PNA) group were commonly
found in the sediments of the Estuary. The PNAs most frequently found at
levels in excess of 10 mg/kg (a level arbitrarily chosen for convenience
in aggregation of the data) and their typical concentrations in mg/kg
were: Fluoroanthene (10-30), benzo(a) anthracene/chrysene (20-50), benzo(a)
pyrene (5-20), 3,4-benzofluoranthene/benzo (k) fluoranthene (20-40),
anthracene/pnenanthrene (15-35), and pyrene (15-30). PNAs were generally
highest in the upper 30 cm of the core samples. The highest concentrations
of PNAs were found in the Central Kinnickinnic Basin, at Walnut Street
and St. Paul Avenue on the Milwaukee River, and at 25^n Street on the
Menomonee River. Levels of PNAs were fairly constant on the Milwaukee River
from Walnut Street to St. Paul Avenue, indicating a source upstream and/or
a diffuse source such as CSOs. In the Menomonee River, PNAs were highest
at 25™ Street and decreased steadily downstream, indicating a source at or
upstream of 25tn Street. Levels of PNAs were fairly low on the Menomonee
Canal. PNA levels were low at Lincoln Avenue on the Kinnickinnic River,
then increased from Kinnickinnic Avenue to the Central Kinnickinnic Basin,
indicating a possible source in that vicinity.
Others
Chlorinated benzene priority pollutants were not detected in the Estuary
sediments except for traces of 1,3 - and 1,4-dichlorobenzene at the
Menomonee River/Canal confluence.
Traces of N-nitrosodiphenylamine were found in the Central Kinnickinnic
Basin. Traces of 3,3-dichlorobenzidine were found at 25tn Street on the
Menomonee River.
Elevated levels of naphthalene were found in the sediments of the Central
Kinnickinnic Basin (9.22 to 24.3 mg/kg). Levels of napthalene at other
locations were low (up to 1 or 2 mg/kg) or nondetectable. There appears
to be a source of naphthalene in the Kinnickinnic Basin area.
Off of Jones Island STP, 4.3 mg/kg of 2,4-dinitrotoluene was found.
19
-------
IV. COMPARISON WITH HISTORICAL SEDIMENT DATA
Sediments in the Estuary were sampled during the summer of 1977 by
Rexnord (Rexnord, 1977). Core samples were obtained and analyzed in
halves or thirds for total solids, total volatile solids, COD, ammonia,
total phosphorus, cadmium, zinc, lead, copper, 8005, nitrate + nitrite,
density, iron, redox, and pH.
shows results for ammonia,
lead to be comparable be-
Comparison of data from comparable locations
total phosphorus, cadmium, copper, zinc, and
tween the 1977 and 1980 surveys. However, levels of total volatile
solids in the 1980 survey were two to three times higher than the 1977
levels; and COD levels for the 1980 survey were only about half of what
was found in 1977. These differences are most likely due to differences
in analytical methods used in the two sets of analyses rather than an
actual change in pollutant conditions, since levels of the other
pollutants were little changed between the two surveys.
The 1977 study concluded that there were no consistent patterns in
pollutant concentrations with depth. In contrast, the 1980 data showed
that most contaminants were higher in the upper portions of the cores.
This difference may be due to differences in the length of cores obtained
in the two surveys as well as differences in the size of the vertical
sections (slices) analyzed.
The 1977 report concluded that levels of pollutants in sediments were
similar in all three rivers of the Estuary, except for zinc and lead
which were two to three times higher in the Kinnickinnic River than in
the other two rivers. The 1980 data generally shows the Menomonee River
has the highest overall sediment pollutant levels, the Kinnickinnic
River has the lowest, while the Milwaukee River is intermediate between
the two.
PCBs
The most comprehensive previous sediment sampling for PCBs in the area
was conducted from May 1975 to April 1976 by the Wisconsin Department of
Natural Resources (Wawrzyn et. al., undated). That study included the
Milwaukee and Kinnickinnic ffTvers, but not the Menomonee River. Surface
grab samples were obtained and analyzed for PCBs and metals.
A comparison of PCB results from comparable sampling sites shows very
little difference between the 1975/1976 study (surface grab sample)
results and the 1980 (core sample) maximum values. This is because the
highest PCB levels in the 1930 study were found at the surface (within
the top 30 or 60 cm of the cores) on the Milwaukee and Kinnickinnic
Rivers.
Surface grab sediment samples were taken in the Kinnickinnic Basin and
the Outer Harbor on March 4, 1980 for a Milwaukee Harbor Commission
dredging permit application. The PCB analyses (Sommer-Frey Laboratories,
Inc.) showed high levels of PCBs (55.6 and 73.3 mg/kg) in the two samples
20
-------
from the Kinnickinnic Basin and in one sample (38 mg/kg) from a mooring
slip (South Slip No. 2) in the Outer Harbor about 2,500" south of the
Inner Harbor Entrance Channel.
Due to the regulatory implications for disposal of dredge spoil contaminat-
ed with such high levels of PCBs, the Harbor Commission had the areas re-
sampled on October 27-29, 1980 by the University of Wisconsin, Great Lakes
Research Facility. The University obtained core samples and sectioned them
in 10 cm vertical sections. The analyses (Raltech Scientific Services)
substantiated the elevated levels in the Outer Harbor (up to 91.5 mg/kg
PCBs), but did not substantiate the levels found in the Kinnickinnic Basin
in the earlier study, finding a maximum of 33.5 mg/kg PCBs in a single 10
cm segment of one core sample. It is unknown why there was such a large
discrepancy between the two sets of samples in the Kinnickinnic Basin. It
should be noted that the USEPA July 29-31/1980 study results agree with
the October 27-29, 1980 University of Wisconsin study results for the
Kinnickinnic Basin samples when the difference in vertical segmentation
of samples is taken into account.
The Milwaukee Metropolitan Sewerage District (MMSD) obtained sediment core
samples at 8 locations in the vicinity of the Jones Island STP outfall on
June 20, 1980. The cores were analyzed for PCBs in halves or thirds.
Concentrations were in the range of 10 to 25 mg/kg total PCBs and tended
to be higher in the upper halves of the cores. The highest concentration
(79.2 mg/kg) was found in the lower half of the core off of South Slip
No. 1. The results of the MMSD survey agree with those of the USEPA
July 29-31, 1980 study.
Other Organic Priority Pollutants
The author was not aware of any comprehensive previous sediment surveys
for organic priority pollutants other than PCBs in the Estuary.
21
-------
REFERENCES
Gruber, D., Milwaukee Metropolitan Sewerage District, personal communication
to Anthony Kizlauskas, U.S. Environmental Protection Agency, Great Lakes
National Program Office, November 10, 1981.
Harleman, O.R.F., and Stolzenbach, K.D., "A Model Study of Thermal Stratific-
ation Produced by Condenser Water Discharge", MIT, Department of Civil
Engineering, Hydrodynamics Laboratory Report No. 107, October 1967.
Milwaukee Metropolitan Sewerage District, Final EIS, Addenda and Revised
Appendix VII, April 1981.
Rexnord, "Water Quality Analysis of the Milwaukee River to Meet PRM 75-34
(PG-61) Requirements", EPA Grant C550772-011, February 8, 1979.
Wawrzyn, W.G., Petri, T.M., and Bode, J.B., "Hazardous and Toxic Substances
in the River Basins of Milwaukee County", Wisconsin Department of Natural
Resources, unpublished, undated.
-------
APPENDIX A
FIELD OBSERVATIONS AND CHEMISTRY DATA
from July 29-31,-1980
U.S. ENVIRONMENTAL PROTECTION AGENCY
Milwaukee Estuary Sediment Study
23
-------
Table A Boring Log
Kinnickinnic, Menomonee, and Milwaukee Rivers
Sampling Dates: July 29, 30, and 31
July 29 station No. 10, 14, 15, and 16
July 30 station No. 1-9
July 31 station No. 11, 12, 17-23
Sampling Equipment
Benthos Gravity Corer Model 2171
Wildco #1725 G10 Grab Sampler
Weather Conditions
July 29 sunny
July 30 rain
July 31 overcast to partly cloudy
There is a possibility of atmospheric contamination on July 30, 1980 due to
high winds and visible particulates.
Station No. 1
Depth of Water: 30 ft
Length of Core: 15 cm
Sediment: hard clay
Color: grey
Odor: —
Station No. 2
Depth of Water: 28 ft
Length of Core: 85 cm
Sediment: mud over clay
Color: mud—dark grey to black; clay—grey
Odor: stale
Station No. 3
Depth of Water: 29 ft
Length of Core: 25 cm
Sediment: mud with a little organic debris
Color: dark grey to black
Odor: earthy
Station No. 4
Depth of Water: 28 ft
Length of Core: 60 cm
Sediment: mud
Color: dark grey to black
Odor: earthy
24
-------
Table A Continued
Station No. 5
Depth of Water: 30 ft
Length of Core: 75 cm
Sediment: mud over clay
Color: mud—black; clay—grey
Odor: hydrocarbons
Sediment contained a little oil. The corer stopped in a hard clay layer.
Station No. 6
Depth of Water: 28 ft
Length of Core: 110 cm
Sediment: mud
Odor: oily, hydrocarbons
Color: black
Station No. 7a
Depth of Water: 28 ft
Length of Core: 60 cm
Sediment: mud
Color: dark grey to black
Odor: oily
Station No. 7b
Depth of water: 28 ft
Length of Core: 55 cm
Sediment: mud
Color: dark grey to black
Odor: oily
Station No. 8
Depth of Water: 27 ft
Length of Core: 60 cm
Sediment: mud
Color: dark grey to black
Odor: oily
Station No. 9
Depth of Water: 18 ft
Length of Core: 45 cm
Sediment: mud
Color: dark grey to black
Odor: earthy
25
-------
Table A Continued
Station No. 10
Depth of Water: 4 ft
Grab Sample
Sediment: mud
Color: black
Odor: earthy
Station No. lla and lib
Depth of Water: 30 ft
Length of Core: lla—80 cm; lib—110 cm
Sediment: mud over clay
Color: mud—black; clay—grey
Odor: oily
Station No. 12
Depth of Water: 28 ft
Length of Core: 54 cm
Sediment: clay
Color: grey
Odor: none
Station No. 13
Depth of Water: 30 ft
Length of Core: 85 cm
Sediment: mud over sandy mud
Color: black
Odor: oily
Station No. 14
Depth of Water: 10 ft
Grab Sample
Sediment: mud
Color: dark grey
Odor: earthy
Station No. 15
Depth of Water: 20 ft
Grab Sample
Sediment: mud with some organic debris
Color: dark grey to black
Odor: earthy
Station No. 16
Depth of Water: 12-24 ft
Grab Sample
Sediment: organic debris (leaves and twigs); also some muddy sand, gravel
Odor: earthy to peaty
Number of Attempts: 9
26
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Table A Continued
Station No. 17
Depth of Water: 28 ft
Length of Core: 90 cm
Sediment: mud over clay
Color: mud—black; clay—grey
Odor: oily, disagreeable
Station No. 18
Depth of Water: 25 ft
Length of Core: 96 cm
Sediment: mud with some oil
Color: black
Odor: hydrocarbons, disagreeable
Station No. 19
Length of Core: 120 cm
Sediment: mud over clay
Color: mud—black; clay—grey
Odor: hydrocarbons, disagreeable
Station No. 20
Length of Core: 25 cm
Sediment: mud over clay
Color: mud—black; clay—grey
Odor: hydrocarbons
Sample could not be taken where indicated on map due to a bridge that
would not cjsen. Sample was taken roughly one block downstream.
Station No. 21
Depth of Water: 28 ft
Length of Core: 115 cm
Sediment: mud over clay
Color: mud—black; clay—grey
Odor: hydrocarbons, disagreeable
Station No. 22
Length of Core: 85 cm
Sediment: mud, oily
Color: black
Odor: hydrocarbons, disagreeable
Station No. 23
Depth of Water: 14 ft
Length of Core: 100 cm
Sediment: mud with top covering of organic matter
Color: black
Odor: hydrocarbons, very disagreeable
27
-------
Table B Sample Numbers Used in this Report and the Sampling
Location and Depth Interval They Represent.
Sample Number
la
2a
2b
2c
3a
4a
4b
5a
5b
5c
6a
6b
6c
6d
7a
7b
7rep.a
7rep.b
8a
8b
9a
9b
10
lla
lib
lie
llrep.a
llrep.b
llrep.c
llrep.d
12a
I2b
Sampling Location
1
2
2
2
3
4
4
5
5
5
6
6
6
6
7
7
7
7
8
8
9
9
10
11
11
11
11 Replicate
11 Replicate
11 Replicate
11 Replicate
12
12
Replicate
Replicate
Depth Interval in Core
(cm)
0-15
0-30
30-60
60-85
0-25
0-30
30-60
0-30
30-60
60-75
0-30
30-60
60-90
90-110
0-30
30-60
0-30
30-50
0-30
30-60
0-30
30-45
Grab
0-30
30-60
60-80
0-30
30-60
60-90
90-110
0-30
30-54
28
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Table B Continued
13a 13 0-30
13b 13 30-60
13c 13 60-85
15 15 Grab
17a 17 0-30
17b 17 30-60
17c 17 60-90
18a 18 0-30
18b 18 30-60
18c 18 60-90
18d 18 90-96
19a 19 0-30
19b 19 30-60
19d 19 90-120
21a 21 0-30
21b 21 30-60
21c 21 60-90
21d 21 90-115
22a 22 0-30
22b 22 30-60
22c 22 60-85
23a 23 0-30
23b 23 30-60
23c 23 60-90
23d 23 90-100
29
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Table C Sediment Concentrations of Some Conventional Pollutants
and Metals in the Milwaukee Harbor Estuary July 29-31,1980.
(All values are mg/kg dry weight unless noted otherwise.)
Parameter
Total Solids (%)
Total Volatile Solids (%)
Chemical Oxygen Demand
Total Kjeldahl Nitrogen
Ammonia Nitrogen
Total Phosphorus
Oil and Grease
Mercury
Lead
Zinc
Manganese
Cobalt
Arsenic
Cadmium
Chromium
Copper
Cyanide
Selenium
Tin
Phenols
la
73.4
1.6
6,800
313
198
565
<1,000
0.10
23.2
80.9
392
10.6
41.8
10.1
91.0
22.2
0.92
2.34
4.0
0.44
2a
30.0
14.4
51,900
1,680
312
5,470
11,400
0.83
252
592
293
5.4
6.70
25.8 ,
1,600
108
4.84
5.53
19
1.23
Sample Number
2b
34.4
16.8
65,400
2,320
460
8,250
14,400
2.30
407
1,950
524
10.5
45.2
73.7
2,380
293
5.88
2.05
65
2.63
2c
53.3
7.6
35,200
975
272
1,530
7,310
1.22
110
657
436
5.4
14.3
20.7
835
93.0
3.20
<2.0
12.4
0.44
3a
34.2
10.4
148,000
4,420
278
141
6,240
0.15
423
423
667
1.6
17.8
11.1
482
105
<2.0
<2.0
18.9
0.70
4a
36.1
10.6
46,500
1,520
82
1,720
6,330
0.58
335
576
511
7.7
33.2
8.4
616
90.0
2.43
<2.0
10.5
1.72
4b
44.0
11.0
44,600
1,100
288
2,080
7,270
0.66
321
554
503
6.9
12.4
8.4
690
103
2.33
<2.0
12.6
0.36
30
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Table C Sediment Concentrations of Some Conventional Pollutants
and Metals in the Milwaukee Harbor Estuary July 29-31,1980.
(All values are mg/kg dry weight unless noted otherwise.)
Parameter
Total Solids (%)
Total Volatile Solids (%)
Chemical Oxygen Demand
Total Kjeldahl Nitrogen
Ammonia Nitrogen
Total Phosphorus
Oil and Grease
Mercury
Lead
Zinc
Manganese
Cobalt
Arsenic
Cadmium
Chromium
Copper
Cyanide
Selenium
Tin
Phenols
5a
47.1
8.6
71,500
1,800
202
386
5,460
0.92
392
582
639
5.6
16.7
13.7
322
110
2.95
<2.0
14.2
0.13
5b
57.1
6.7
10,900
1,160
254
639
<1,000
0.16
89
106
778
2.4
12.8
5.8
15
33
<1.8
<2.0
<8.0
0.12
Sample Number
5c
56.5
4.3
14,000
1,110
334
533
<1,000
<0.1
30
74
859
0.9
5.7
5.4
36
25
<1.7
<2.0
<8.0
0.39
6a
43.8
12.6
68,600
1,350
336
1,740
6,470
1.48
534
925
598
8.5
40.6
17.8
386
154
12.6
<2.0
25.0
0.14
6b
43.6
14.5
88,000
1,370
438
1,160
16,400
1.83
436
1,040
409
2.0
38.2
19.4
330
192
18.3
<2.0
19.6
0.34
6c
45.6
14.8
97,200
2,650
360
1,130
14,700
1.92
477
1,730
425
7.2
69.4
45.7
423
271
36.7
<2.0
23.2
0.46
6d
52.4
12.4
63,600
2,400
372
954
7,700
2.05
324
730
478
7.2
61.4
14.7
355
140
15.5
<2.0
17.6
0.29
31
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Table C Sediment Concentrations of Some Conventional Pollutants
and Metals in the Milwaukee Harbor Estuary July 29-31,1980.
(All values are mg/kg dry weight unless noted otherwise.)
Parameter
Total Solids (%)
Total Volatile Solids (%)
Chemical Oxygen Demand
Total Kjeldahl Nitrogen
Ammonia Nitrogen
Total Phosphorus
Oil and Grease
Mercury
Lead
Zinc
Manganese
Cobalt
Arsenic
Cadmium
Chromium
Copper
Cyanide
Selenium
Tin
Phenols
7a
49.6
9.4
46,400
1,230
151
1,080
3,800
0.83
298
595
500
5.7
21.0
11.6
234
94
3.95
<2.0
<8.0
0.20
7b
62.4
8.4
31,700
966
152
561
3,800
0.86
160
276
265
3.21
17.3
6.2
156
69
5.08
<2.0
<8.0
0.14
Sample Number
7rep.a
37.9
10.8
53,300
1,480
219
1,730
10,100
1.09
417
676
427
7.69
' 35.0
13.4
290
129
4.49
<2.0
35.5
0.24
7rep.b
68.7
6.1
21,900
450
96
358
2,000
0.66
127
165
223
3.52
8.8
5.1
136
40
6.43
<2.0
<8.0
0.07
8a
46.3
10.5
44,300
1,490
244
890
12,600
0.47
838
919
643
5.8
13.6
12.8
140
150
3.67
<2.0
48.1
0.65
8b
51.5
11.1
41,900
656
262
604
15,900
0.63
1,080
999
601
8.11
28.5
14.7
152
137
<1.9
<2.0
40.8
0.49
9a
67.2
7.0
21,500
632
177
726
2,420
0.40
659
564
388
5.3
14.4
7.1
64
111
<1.5
<2.0
10.6
0.52
9b
58.
10.
41,60
1,640
463
1,060
4,940
0.77
500
664
470
7.37
12.0
13.3
87
114
3.24
<2.0
23.2
0.45
32
-------
Table C Sediment Concentrations of Some Conventional Pollutants
and Metals in the Milwaukee Harbor Estuary July 29-31,1980.
(All values are ing/kg dry weight unless noted otherwise.)
Parameter
Total Solids (%)
Total Volatile Solids (%)
Chemical Oxygen Demand
Total Kjeldahl Nitrogen
Ammonia Nitrogen
Total Phosphorus
Oil and Grease
Mercury
Lead
Zinc
Manganese
Cobalt
Arsenic
Cadmium
Chromium
Copper
Cyanide
Selenium
Tin
Phenols
10
66.9
3.5
19,000
<220
176
386
3,980
0.21
608
419
429
3.73
4.2
9.6
54
77
<1.5
<2.0
21.5
1.27
lla
37.8
12.2
38,600
1,530
280
1,670
7,900
0.70
467
485
590
6.73
6.9
11.6
424
121
<2.5
<2.0
32.6
0.16
Sample Number
lib
69.0
4.0
12,500
1,020
146
393
<1,000
<0.09
28
70
537
2.12
0.8
<1.00
17
17
<1.4
<2.0
<8.0
<0.06
He
59.2
5.2
19,000
1,220
164
512
<1,000
<0.1
34
77
798
3.59
1.8
<1.00
20
21
<1.6
<2.0
<8.0
0.76
llrep.a
51.1
6.2
28,400
1,470
219
1,510
2,960
0.37
277
343
691
4.39
12.0
5.33
355
80
<1.9
<2.0
<8.0
0.94
llrep.b
63.1
4.6
15,200
1,140
184
525
998
<0.1
37
60
709
2.71
4.0
<1.00
22
18
<1.6
<2.0
<8.0
0.51
llrep.c
57.7
5.1
19,900
1,200
218
693
<1,000
<0.1
44
85
819
5.56
1.5
<1.00
28
23
<1.7
<2.0
<8.0
0.68
llrep.d
56.3
5.0
18,000
927
243
696
<1,000
<0.1
40
94
831
4.00
3.6
<1.00
43
27
<1.7
<2.0
<8.0
0.73
33
-------
Table C Sediment Concentrations of Some Conventional Pollutants
and Metals in the Milwaukee Harbor Estuary July 29-31,1980.
(All values are mg/kg dry weight unless noted otherwise.)
Parameter
Total Solids (%)
Total Volatile Solids (%)
Chemical Oxygen Demand
Total Kjeldahl Nitrogen
Ammonia Nitrogen
Total Phosphorus
Oil and Grease
Mercury
Lead
Zinc
Manganese
Cobalt
Arsenic
Cadmium
Chromium
Copper
Cyanide
Selenium
Tin
Phenols
12a
57.6
6.6
27,000
1,110
56
677
<1,000
<0.1
36
90
801
3.32
5.3
<1.00
18
23
<1.6
<2.0
<8.0
0.52
12b
65.3
19.2
21,600
1,290
104
492
<1,000
<0.09
38
73
892
3.60
2.7
<1.00
27
22
<1.5
<2.0
<8.0
0.76
Sample Number
13a
36.0
9.9
38,500
2,000
164
2,120
L 8,420
1.39
727
642
738
4.87
14.1
7.28
1,080
165
<2.6
<2.0
64.6
0.22
13b
37.7
12.2
48,200
3,150
257
2,630
15,000
2.39
636
732
579
6.20
20.6
9.26
2,250
226
<1.6
<2.0
114
0.32
13c
49.4
10.1
56 ,800
2,000
186
1,410
8,060
1.88
533
661
537
5.77
25.3
7.18
311
207
<2.0
<2.0
66.9
0.26
15
39.6
8.8
46,100
2,740
172
1,300
12,200
0.61
562
406
431
3.90
17.7
4.15
130
117
<2.5
<2.0
8.8
1.56
34
-------
Table C Sediment Concentrations of Some Conventional Pollutants
and Metals in the Milwaukee Harbor Estuary July 29-31,1980.
(All values are mg/kg dry weight unless noted otherwise.)
Parameter
Total Solids (%)
Total Volatile Solids (%)
Chemical Oxygen Demand
Total Kjeldahl Nitrogen
Ammonia Nitrogen
Total Phosphorus
Oil and Grease
Mercury
Lead
Zinc
Manganese
Cobalt
Arsenic
Cadmi urn
Chromium
Copper
Cyanide
Selenium
Tin
Phenols
17a
51.4
7.8
37,600
1,090
185
1,260
6,530
0.66
529
322
402
8.77
11.6
10.9
267
120
3.21
<2.0
35.1
0.19
17b
57.8
11.8
49,600
1,910
223
1,530
<1,000
1.06
349
509
578
6.62
24.4
11.4
298
174
3.34
<2.0
97.9
0.28
Sample Number
17c
54.6
9.1
39,900
2,800
253
1,160
1,960
0.56
310
426
668
5.81
15.6
8.27
227
150
2.38
<2.0
30.6
0.22
18a
44.6
9.3
47,300
1,980
215
1,460
5,230
0.82
448
564
625
5.54
19.3
10.2
411
217
2.20
<2.0
49.1
0.27
18b
50.6
8.4
43,800
1,940
302
1,410
6,070
1.00
448
554
599
6.24
19.6
7.45
445
187
2.65
<2.0
64.3
0.18
18c
57.0
10.0
55,000
2,300
240
768
7,960
'1.24
370
528
497
5.51
21.5
7.44
405
168
<1.8
<2.0
17.4
0.25
18d
55.8
8.3
102,000
2,810
265
366
10,050
2.57
395
605
460
6.29
26.6
6.75
461
156
<1.8
<2.0
49.1
0.30
35
-------
Table C Sediment Concentrations of Some Conventional Pollutants
and Metals in the Milwaukee Harbor Estuary July 29-31,1980.
(All values are mg/kg dry weight unless noted otherwise.)
Parameter
Total Solids (%)
Total Volatile Solids (%)
Chemical Oxygen Demand
Total Kjeldahl Nitrogen
Ammonia Nitrogen
Total Phosphorus
Oil and Grease
Mercury
Lead
Zinc
Manganese
Cobalt
Arsenic
Cadmium
Chromium
Copper
Cyanide
Selenium
Tin
Phenols
19a
36.4
10.5
84,500
4,040
511
591
19,400
1.06
521
711
668
8.11
38.1
11.7
521
282
4.04
<2.0
13.2
0.22
19b
42.2
14.9
76,600
3,390
386
829
8,630
2.96
487
793
808
6.70
44.7
19.1
543
216
<2.0
<2.0
25.5
0.36
Sample Number
19d
54.3
8.9
•36,500
1,500
381
285
1,830
0.60
173
330
735
3.61
37.9
9.72
167
86
<1.8
<2.0
<8.0
0.17
21a
43.4
9.3
25,900
4,100
228
440
10,500
1.00
616
702
550
8.40
10.0
21.4
425
121
<2.3
<2.0
19.2
0.37
21b
49.8
9.6
45,300
2,450
319
1,070
15,300
0.80
604
621
506
9.46
11.8
15.3
531
178
4.92
<2.0
<8.0
0.32
21c
57.2
7.0
80,900
1,080
248
350
10,200
0.66
495
472
684
3.66
31.0
13.8
369
144
2.36
<2.0
12.6
0.33
21d
55.1
6.3
84,800
2,270
210
281
<1,000
<0.1
59
86
1,220
6.17
7.80
8.63
43
19
<1.8
<2.0
<8.0
0.33
36
-------
Table C Sediment Concentrations of Some Conventional Pollutants
and Metals in the Milwaukee Harbor Estuary July 29-31,1980.
(All values are mg/kg dry weight unless noted otherwise.)
Parameter
Total Solids (%)
Total Volatile Solids (%}
Chemical Oxygen Demand
Total Kjeldahl Nitrogen
Ammonia Nitrogen
Total Phosphorus
Oil and Grease
Mercury
Lead
Zinc
Manganese
Cobalt
Arsenic
Cadmium
Chromium
Copper
Cyanide
Selenium
Tin
Phenols
22a
47.9
9.6
45,600
3,850
242
720
11,100
0.74
665
637
588
23.8
18.4
15.7
214
159
7.72
<2.0
8.9
0.51
22b
60.2
12.1
42,400
1,840
312
498
10,500
0.72
584
568
823
23.8
42.5
21.6
147
153
6.16
<2.0
18.8
3.51
Sample Number
22c
63.5
13.4
45,600
2,660
431
480
9,980
2.06
479
544
538
2.86
24.6
16.6
227
199
4.80
<2.0
23.2
0.67
23a
33.8
13.2
59,900
7,680
1,250
1,390
16,200
0.90
729
775
815
3.50
17.0
34.4
199
188
11.5
<2.0
10.8
0.86
23b
41.4
13.8
51,900
6,500
471
1,230
14,800
0.52
683
569
754
4.85
3.00
25.1
154
228
8.33
<2.0
10.0
1.79
23c
48.5
11.1
175,000
870
645
1,170
8,570
0.80
810
111
715
6.56
16.4
17.5
208
247
6.58
<2.0
14.4
0.31
23d
46.0
/
12.1
67,600
1,690
452
1,400
23,300
1.45
1,180
1..140
914
4.25
15.1
25.2
270
307
9.87
<2.0
31.6
0.26
-------
Table D Organic. Compounds Sought and Typical Detection Limits.
(Actual detection limits for individual samples may vary as a
function of interferences present, aliquot size, degree of
pre-concentration, etc.)
Compound Typical Detection Limit (mg/kg)
Pesticides
aldrin 0.01
dieldrin .0.01
chlordane 0.01
4,4'-DDT 0.03
4,4'-DDE 0.01
4,4'-DDD 0.01
alpha-endosulfan 0.01
beta-endosulfan 0.01
endrin 0.02
heptachlor 0.01
heptachlor epoxide 0.01
alpha-BHC 0.01
beta-BHC 0.01
gamma-BHC 0.01
delta-BHC 0.01
PCB-1242 0.01
PCB-1254 0.01
PCB-1221 0.01
PCB-1232 0.01
PCB-1248 0.01
PCB-1260 0.01
PCB-1016 0.01
toxaphene 0.01
Acid Compounds
2,4,6-trichlorophenol 0.1
p-chloro-m-cresol 0.1
2-chlorophenol 0.1
2,4-dichlorophenol 0.1
2,4-dimethylphenol 0.1
2-nitrophenol 0.1
4-nitrophenol 0.1
2,4-dinitorphenol 1.0
4,6-dinitro-o-cresol 0.2
pentachlorophenol 0.1
38
-------
Table D Continued
Base/Neutral Compounds
acenaphthene 0.5
benzidine 2
1,2,4-trichlorobenzene 0.1
hexachlorobenzene O.l
hexachloroethane 0.1
bis(2-chloroethyl)ether 0.1
1,2-dichlorobenzene 0.1
1,3-dichlorobenzene 0.1
1,4-dichlorobenzene 0.1
3,3'-dichlorobenzidine 0.1
2,4-dinitrotoluene 0.2
2,6-dinitrotoluene 0.1
1,2-diphenylhydrazine 0.1
(as azobenzene)
fluoroanthene 0.1
4-chlorophenyl phenyl ether 0.1
4-brotnophenyl phenyl ether 0.1
bis(2-chloroisopropyl)ether 0.1
bis(2-chloroethoxy)methanc 0.1
hexachlorobutadiene 0.1
hexachlorocyclopentadiene 0.1
isophorone 0.1
naphthalene 0.5
nitrobenzene 0.1
N-nitrosodiphenylamine 0.1
N-nitrosodi-n-propylamine 0.1
bis(2-ethylhexyl)phthalate 0.1
butyl benzyl phthalate O.l
di-n-butyl phthalate 0.1
di-n-octyl phthalate 0.1
diethyl phthalate 0.1
dimethyl phthalate 0.1
benzo(a)anthracene/chrysene 0.1
benzo(a)pyrene 0.5
3,4-benzofluoranthene/benzo(k)fluoranthene 0.5
acenaphthylene 0.5
anthracene/phenanthrene 0.5
benzo(ghi)perylene 0.5
fluorene 0.5
dibenzo(a,h)anthracene 0.5
indeno(l,2,3-cd)pyrene 0.5
pyrene 0.5
2,3,7,8-tetrachlorodibenzo- 0.1
p-dioxin
-------
Parameter
Table E Sediment Concentrations of Some Organic Pollutants
in the Milwaukee Harbor Estuary July 29-31, 1980.
(All values are mg/kg dry weight)
Sample Number
aldrin
dieldrin
chlordane
endrin
4,4'-DDE
alpha-BHC
heptachlor
gamma-BHC
delta-BHC
pentachlorophenol
Aroclor 1254
Aroclor 1248
Total PCBs
toxaphene
2,4-dinitrotoluene
fluoroanthene
bi s(2-ethyl hexyl ) phthal ate
di-n-butyl phthal ate
di ethyl phthal ate
benzo(a) anthracene/
rhryspnp
benzo(a) pyrene
anthracene/ phenanthrene
phenanthrene
indeno(l ,2,3-cd) pyrene
pyrene
fluorene
*only analyzed for PUtss.
la
0.02
0.01
0.40
0.66
1.06
1.1
0.7
0.3
0.7
2a
0.06
0.44
0.18
0.03
0.11
3.50
4.90
8.40
13
43
1.2
1.5
11
17
0.5
3.2
3.5
13
2b
0.01
0.03
0.02
1.10
0.06
14.0
33.0
47.0
4.3
11
28
9.3
12
3.3
0.7
12
0.9
2c
0.33
0.02
0.19
0.02
0.12
4.6
6.20
7.40
13.60
1.4
8.5
0.7
0.7
2.8
3.0
0.6
0.7
3a*
<0.4
<0.5
<0.9
4a
0.20
0.01
0.08
4.00
4.10
8.10
2.10
7.0
11
6.7
6.5
1.8
3.6
7.5
4b
0.07
0.25
0.03
0.12
5.40
8.70
14.10
6.0
9.6
5.4
22
1.6
1.8
6.5
40
-------
Parameter
Table E Sediment Concentrations of Some Organic Pollutants
in the Milwaukee Harbor Estuary July 29-31, 1980.
(All values are mg/kg dry weight)
Sample Number
Aroclor 1242
Aroclor 1254
Aroclor 1221
Aroclor 1232
Aroclor 1248
Total PCBs
acenaphthene
fluoroanthene
N-ni trosodi phenyl ami ne
naphthalene
bis(2-ethylhexyl) phthalat<
di-n-butyl phthalate
di ethyl phthalate
benzo(a) pyrene
3,4 Denzoriuoranthene/
benzo (k) fluoranthene
benzo (a)anthracene/
chrysene
acenaphthylene
anthracene/phenanthrene
benzo(ghi) perylene
fluorene
dibenzo(a.h) anthracene
indeno(l ,2,3-cd) pyrene
pyrene
5a*
0.5
0.7
1.0
1.0
5.7
8.9
5b*
0.49
1.19
1.68
5c*
0.06
0.08
0.14
6a
2.67
2.92
5.59
23.2
5.68
5.99
0.36
0.33
12.4
25.0
25.7
1.22
15.3
7.27
0.90
5.67
7.47
15.6
6b
1.50
1.50
1.06
42.5
12.7
3.32
23.1
39.1
48.8
1.89
24.3
13.7
2.21
11.6
15.1
28.5
6c
0.81
0.51
1.32
4.01
66.9
24.3
41.3
50.9
76.9
4.34
34.9
22.3
2.98
20.6
21.8
48.1
6d
0.09
0.09
0.18
2.01
30.4
0.6
9.22
17.2
25.2
40.9
2.28
20.4
8.78
1.77
10.9
9.67
22.9
'
*only analyzed for PCBs,
-------
Table E Sediment Concentrations of Some Organic Pollutants
in the Milwaukee Harbor Estuary July 29-31, 1980.
(All values are mg/kg dry weight)
Parameter
Aroclor 1254
Aroclor 1248
Total PCBs
fluoroanthene
acenaphthene
naphthalene
bis(2-ethylhexyl) phthalat
butyl benzyl phthalate
di-n-butyl phthalate
di-n-octyl phthalate
diethyl phthalate
benzo(a) pyrene
3,4 benzof 1 uoranthene/
benzo(k) fluoranthene
benzo(a) anthracene/
chr.ysene
acenaphthylene
anthracene/phenanthrene
benzo(ghi) perylene
fl uorene
dibenzo(a.h) anthracene
indeno(l ,2,3-cd) pyrene
pyrene
Sc
7a*
8.40
1.82
10.22
:*
jmple Nun
7b*
0.37
0.37
iber
7rep.a*
6.09
6.09
7rep.b*
<0.03
<0.04
<0.07
8a
4.86
4.86
48.4
2.84
0.61
8.14
0.97
0.32
0.52
0.53
28.3
31.1
60.2
0.81
25.5
6.75
2.01
6.04
8.59
35.3
8b
4.05
4.05
25.3
1.19
0.24
2.52
0.45
0.17
11.5
15.2
28.4
0.43
15.7
4.23
1.46
3.39
5.23
20.0
9a*
<0.6
<0.8
<1.4
9b*
<0.6
<0.7
<1.3
''only analyzed for PCBs
42
-------
Table E Sediment Concentrations of Some Organic Pollutants
in the Milwaukee Harbor Estuary July 29-31, 1980.
(All values are mg/kg dry weight)
Parameter
Aroclor 1248
Total PCBs
acenaphthene
fl uoranthene
diethyl phthalate
benzo(a) pyrene
3, 4- benzofl uoranthene/
ben?o(k) flunranthpne
benzo(a) anthracene/
chryspnp
acenaphthylene
anthracene/ phenanthrene
benzo(ghi) perylene
fluorene
benzo(a,h) anthracene
indeno(l ,2,3-cd)pyrene
pyrene
S
10
5.06
5.06
0.32
8.02
0.26
2.23
3.3?
9.40
0.11
5.41
1.11
0.48
0.70
1.19
7.96
ample Nui
lla*
5.10
5.10
nber
lib*
0.11
0.11
lie*
0.05
0.05
11
rep. a*
4.7
4.7
11
rep.b*
0.41
0.41
11
rep.c*
0.15
0.15
11
rep.d1
0.07
0.07
*only analyzed for PCBs.
43
-------
Parameter
Table E Sediment Concentrations of Some Organic Pollutants
in the Milwaukee Harbor Estuary July 29-31, 1980.
(All values are mg/kg dry weight)
Sample Number
Aroclor 1248
Total PCBs
2, 4-dimethyl phenol
acenaphthene
fluoroanthene
naphthalene
butyl benzyl phthalate
bis(2-ethylhexyl) phthalat<
di-n-butyl phthalate
diethyl phthalate
di-n-octyl phthalate
benzo(a) pyrene
,t-ueri£UT i uur dMLiient;/
benzo(k) fluoranthene
enzu ^a; ariLnracene/
chrysene
acenaphthylene
anthracene/phenanthrene
benzo(ghi) perylene
fluorene
dibenzo(a.h) anthracene
indeno(l ,2,3-cd) pyrene
pyrene
iza*
0.04
0.04
i
IZD*
0.07
0.07
Ua
22
22
2.58
46.0
2.09
16.7
0.85
1.03
22.4
37.4
78.3
0.52
21.6
7.93
2.44
5.61
8.13
38.1
Ub
32
32
0.41
0.78
29.2
0.45
6.55
0.16
0.29
12.8
21.3
46.5
0.54
15.5
8.64
1.11
5.79
5.76
23.5
IJC
2.1
2.1
0.88
15.4
0.92
1.56
0.17
0.88
5.42
7.72
21.6
0.46
11.8
2.29
1.21
1.39
2.55
10.2
lb
8.8
8.8
2.47
64.7
0.70
0.55
8.94
0.80
1.34
0.26
19.1
31.8
82.9
0.56
36.2
7.78
2.64
6.25
8.96
48.9
*only analyzed for PCBs
44
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Table E Sediment Concentrations of Some Organic Pollutants
in the Milwaukee Harbor Estuary July 29-31, 1980.
(All values are rag/kg dry weight)
Parameter
Aroclor 1248
Total PCBs
acenaphthene
1 ,3-dichlorobenzene
1 ,4-dichlorobenzene
fluoroanthene
naphthalene
bis(2-ethylhexyl) ohthalat<
di-n-butyl phthalate
di ethyl phthalate
benzo(a) pyrene
3,4-benzofluoranthene/
benzo(k) fluoranthene
benzo(a) anthracene/
chrysene
acenaphthylene
anthracene/phenanthrene
benzo(qhi) perylene
fluorene
dibenzo(a.h) anthracene
ideno(l ,2,3-cd) pyrene
pyrene
Sa
17a
2.9
2.9
0.45
16.8
0.40
i 4.70
0.16
0.42
5.92
13.4
19.5
0.41
6.85
3.21
0.70
8.09
7.64
8.30
mple NUIT
17b
2.1
2.1
0.78
0.18
0.79
18.1
0.95
2.06
0.14
0.18
6.59
13.7
2.05
0.39
9.55
2.00
1.05
3.70
3.66
11.9
iber
17c
0.60
0.60
0.32
10.3
0.47
0.83
0.10
0.14
3.90
7.20
19.4
0.20
7.19
2.78
0.64
2.50
1.75
8.22
18a*
3.0
3.0
18b*
2.7
2.7
18c*
7.8
7.8
18d*
8.5
8.5
*only analyzed for PCBs.
-------
Table E Sediment Concentrations of Some Organic Pollutants
in the Milwaukee Harbor Estuary July 29-31, 1980.
(All values are rng/kg dry weight)
Parameter
Aroclor 1254
Aroclor 1248
Total PCB's
2,4-dimethylphenol
acenaphthene
fluoroanthene
naphthalene
cns(z-ethylhexyl
phthalate
di-n-butyl phthalate
di-n-octyl phthalate
diethyl phthalate
benzo(a) pyrene
3,4-benzofl uoranthene/
benzo(k) fluoranthene
benzo(a) anthracene/
chrysene
acenaphthylene
anthracene/phenanthrene
benzo(ghi) perylene
fluorene
dibenzo(a,h) anthracene
indeno(l ,2,3-cd) pyrene
pyrene
So
19a
2.4
. 2.4
0.14
0.51
12.5
0.57
5.10
0.18
0.14
0.45
5.55
9.97
19.3
0.36
8.09
4.79
0.78
2.59
2.92
10.5
*only ar
imple Nun
19b
1.9
3.6
5.5
0.80
14.3
1.07
3.64
4.99
10.4
15.0
0.70
9.45
3.37
1.24
10.2
8.37
8.58
lalyzed 1
iber
19d
0.49
0.49
0.21
*
2.65
0.27
0.46
0.10
0.35
1.12
2.44
4.17
0.14
1.39
0.54
0.25
1.33
1.32
1.83
ror PCBs
21 a*
3.6
6.7
10.3
21 b*
2.9
7.1
10.0
21 c*
3.6
3.6
21 d*
0.07
0.07
,
46
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Table E Sediment Concentrations of Some Organic Pollutants
in the Milwaukee Harbor Estuary July 29-31, 1980.
(All values are mg/kg dry weight)
Parameter
aldrin
4,4'-DDT
4,4'-DDE
4,4'-DDD
Aroclor 1248
Total PCBs
heptachlor epoxide
acenaphthene
3,3 -dichlorobenzidine
fluoroanthene
naphthalene
bis (2-ethylhexyl)
phthalate
butyl benzyl phthalate
di-n-butyl phthalate
di-n-octyl phthalate
di ethyl phthalate
benzo(a^ jDyrene
3,4-benzofl uoranthene/
benzo(k) fl uoranthene
benzo(a) anthracene/
chrysene
acenaphthylene
anthracene/phenanthrene
benzo(ghi) perylene
fluorene
d ibenzo( a, h) anthracene
indeno(l ,2,3-cd) pyrene
pyrene
22a
3.2
3.2
2.23
44.3
0.59
15.0
0.50
0.32
1.33
15.6
26.0
49.8
1.69
31.6
5.90
2.35
3.75
6.86
32.8
22b
3.6
3.6
1.93
32.3
0.70
7.44
9.29
22.2
2.87
0.84
21.5
4.74
2.49
11.4
9.82
17.0
t
22c
3.7
3.7
3.55
37.6
1.80
0.22
0.27
1.00
15.8
24.0
51.0
1.04
39.9
6.05
4.58
4.60
5.35
27.4
>ample f
23a
1.3
1.3
11.9
84.6
41.3
2.1
8.6
35.4
40.9
117
63.9
14.5
4.27
8.49
14.2
88.0
lumber
23b
0.17
0.10
0.05
<0.8
<0.8
1.16
34.2
0.26
9.93
1.65
0.47
0.30
9.02
21.9
31.4
0.50
20.5
3.46
2.83
8.61
8.20
18.9
23c
0.07
0.16
0.10
0.08
<0.8
<0.8
2.06
0.2
39.5
0.32
11.6
0.15
0.26
0.24
12.9
21.2
48.8
0.93
32.2
7.24
2.50
5.23
6.22
30.4
23d
0.32
0.39
0.13
<0.8
<0.8
0.04
2.74
49.4
0.28
9.70
0.14
0.33
0.22
17.2
29.1
64.7
1.32
37.6
11,0
3.50
8.08
9.04
38.8
47
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APPENDIX B
GUIDELINES FOR THE POLLUTIONAL CLASSIFICATION
OF GREAT LAKES HARBOR SEDIMENTS
U.S. ENVIRONMENTAL PROTECTION AGENCY
REGION V
CHICAGO, ILLINOIS
APRIL, 1977
48
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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 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. 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 polychlorinated biphenyls (PCB's).
3. Due to the documented bioaccumulation of mercury and PCB's, rigid
limitations are used which override all other considerations.
Sediments are classified as heavily polluted, moderately polluted, or non-
polluted 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 elutriate test results, source of contamination, particle
size distribution, benthic mecroinvertebrate populations, color, and odor
are also considered. These factors are interrelated in a complex manner
and their intepretation is necessarily somewhat subjective.
The following ranges used to classify sediments from Great Lakes harbors
are based on compilations of data from over 10U different harbors since
1967.
NQNPOLLUTED MODERATELY POLLUTED HEAVILY POLLUTED
Volatile Solids (%) <5 b - 8 >8
COD (mg/kg dry weight) <4Q,000 40,000-80,000 >80,000
TKN " " " <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 " " " <90 90-200 >200
49
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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
Cadmium
Chromium
Barium
Copper
*Lower limits not established
The guidelines stated below for mercury and PCB's are based upon the best
available information and are subject to revision as new information be-
comes available.
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 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. If the guideline values are exceeded, the sediments
are classified as polluted and unacceptable for open lake disposal no
matter what the other data indicate.
<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
50
-------
POLLUTED
Mercury _> 1 mg/kg dry weight
Total PCB's 2. 10 NQ/kg dry weight
The pollutional classification of sediments with total PCB concentrations
between 1.0 mg/kg 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,
centrifuged, and filtered through a 0.45 u filter. The
filtered water (elutriate water) is then chemically analyzed.
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 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 classific-
ations. 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. Sediments faithfully reflect the inputs of paper
mills, steel mills, sewage discharges, and heavy industry.
Many sediments may have moderate or high concentrations of
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 may
be given in the range values for TKN, COD, and volatile solids
provided that toxic materials are not also persent.
51
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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 survey.
Texture: A general rule is the finer the material the more
polluted it is. Sands and gravels usually have low concentra-
tions of pollutants while silts usually have higher concentra-
tions. Silts are frequently carried from polluted upstream
areas, whereas sand usually comes from lateral draft along the
shore of the lake. Once again, this general rule can have ex-
ceptions 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 deoote 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 estalishment
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.
Oily Material: This almost 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 sediments. A
moderate concentration of oligochaetes or other tolerant organisms
frequently characterizes an acceptable sample. The worst case
exists when there is a complete lack or very "limited number of
organisms. This may indicate a toxic condition.
52
-------
In 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 which may support only a few organisms. Silty
material, on the other hand, usually provides a good habitat for
sludgeworms, leeches, fingernail clams, and perhaps, amphipods.
Material that is frequently disturbed by ship's propellers provides
a poor habitat.
53
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REFERENCES
1. Jensen, S., and Jernelov, A., "Biological Methylation of Mercury in
Aquatic Organisms,".Nature, 223, August 16, 1969 pp 753-754.
2. Magnuson, J.J., Forbes, A., and Hall, R., "Final Report - An Assess-
ment of the Environmental Effects of Dredged Material Disposal in
Lake Superior - Volume 3: Biologial Studies," Marine Studies Center,
University of Wisconsin, Madison, Mar.ch 1976.
3. 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,
Tennessee.
54
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TECHNICAL REPORT DATA
oni or. tht rorrji before compltiinf
i REPORT NO
905/4-86-001
3 RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
Report on an investigation of sediment contamination
The Milwaukee Estuary, Wisconsin Sampled July 29-31,
1980.
6. REPORT DATE
March 1986
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO.
Anthony G. Kizlauskas
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Great Lakes National Program Office
U.S. Environmental Protection Agency
536 South Clark Street
Chicago, Illinois 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 South Clark Street
Chicago, Illinois 60605
13. TYPE OF REPORT AND PERIOD COVERED
FINAL
14. SPONSORING AGENCY CODE
Great Lakes National Program
Office-USEPA, Region V
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Sediment samples were collected at 23 representative locations in the Milwaukee
Estuary, Wisconsin, July 29-31, 1980. Analyses of the samples showed high con-
centrations of inorganic pollutants and heavy metals, and detectable levels of
a number of organic priority pollutants. Contaminant concentrations are generally
highest in the upper sediment layers, indicating probably recent input of pollu-
tants to the estuary. Hajor source areas for various pollutants were identified.
Although most industrial dischargers discharge to the Jones Island Municipal
Sewage Treatment Plant via sanitary sewers, the nature and degree of sediment con-
tamination in the estuary is comparable to major industrialized Great Lakes harbors
subject to large numbers of direct industrial discharges. During rainfall events,
it is possible that process wastes mixed with storm water and sewage are discharged
directly to the estuary through combined sewer overflows.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATi Field/Group
Sediment, Conventional Pollutants,
Organic Contaminants, Metals,
Pesticides, PCB,
Milwaukee River, Menomonee River,
Kinnickinnic River.
1,3. DISTRIBUTION STATEMENT
Document is available through the
National Technical Information Service,
Springfield, VA. 22161
19 SECURITY CLASS (This Report)
Unclassifed
21. NO. OF PAGES
62
20 SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
~tf US GOVERNMENT PRINTING OFFICE 1986—643-254/757
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